Co-reporter:Xiaolu Wang, Mengjia Liu, Yuqing Wang, Hongyan Fan, Jie Wu, Chao Huang, and Hongwei Hou
Inorganic Chemistry November 6, 2017 Volume 56(Issue 21) pp:13329-13329
Publication Date(Web):October 16, 2017
DOI:10.1021/acs.inorgchem.7b02106
To develop coordination polymers (CPs) as catalysts to selectively catalyze the reaction of C–H bond activation of arylalkanes to their homologous ketones, three new Cu(I)-based coordination polymers (CuI–CPs) [CuI(aas-TPB)]n (1), [CuBr(ass-TPB)CH3CN]n (2), and {[Cu(ass-TPB)]Cl}n (3) (TPB = N,N,N-tris(3-pyridinyl)-1,3,5-benzenetricarboxamide) were synthesized. Structural variations from a herringbone fashion one-dimensional framework of 1 to a two-dimensional framework of 2 containing a 48-membered macrocycle and a cationic three-dimensional framework of 3 filled with Cl– anions were observed arising from the different halogen ions (I–, Br–, and Cl–). 1–3 were used as the green heterogeneous catalysts to catalyze direct C–H bond activation reactions of arylalkanes to ketones under mild reaction conditions with water as solvent. Handy product separation, convenient reaction procedures, and recyclability of these catalysts make the catalytic system fascinating. Moreover, the CuI–CPs performed the reaction with high regioselectivity due to the unique spatial confinement effect of CPs.
Co-reporter:Yazhen Wang, Feihu Yu, Xiao Han, Ming Li, Yue Tong, Jie Ding, and Hongwei Hou
Inorganic Chemistry May 15, 2017 Volume 56(Issue 10) pp:5953-5953
Publication Date(Web):April 27, 2017
DOI:10.1021/acs.inorgchem.7b00653
In this work, we first found a surprising solvothermal reaction for direct dinitration of quinoline derivative. To explore the application in direct nitroquinoline synthesis, this reaction was subsequently modified as an equivalent reaction in a Schlenk tube. More significantly, after a constant attempt, nitrated derivative was obtained in optimized condition with a zinc(II) sulfate catalyst, where some substrates with strong electron-withdrawing group were first nitrated by a directly catalyzed condition. This new zinc(II)-catalyzed aromatic C–H activation reaction is the first example of direct dinitration by a single catalyst, which will be a new facile and environmentally friendly strategy to access synthetically useful nitroquinoline derivative.
Co-reporter:Chao Huang, Xiao Han, ZhiChao Shao, Kuan Gao, Mengjia Liu, Yanjie Wang, Jie Wu, Hongwei Hou, and Liwei Mi
Inorganic Chemistry May 1, 2017 Volume 56(Issue 9) pp:4874-4874
Publication Date(Web):April 7, 2017
DOI:10.1021/acs.inorgchem.6b03091
A series of solvent-induced Ag-based coordination polymers (CPs) (1–3), which were synthesized by regulating the size, shape, and polarity of solvent molecules (EtOH, iPrOH, 1,4-dioxane) as structure-directing agents, has been used as heterogeneous catalysts to explore how the metal–metal bonds could serve as cooperative catalysis for tandem acylation–Nazarov cyclization reaction to prepare cyclopentenone[b]pyrroles frameworks. Structural conversions from a three-dimensional (3D) framework of 1 to the structure of 2 with Ag–Ag–Ag bonds and to the two-dimensional (2D) framework of 3 with Ag–Ag bonds, arising from the different sizes, shapes, and polarities of the solvent molecules, were observed. Futhermore, the effective cooperative catalysis for tandem acylation–Nazarov cyclization reaction has been evidenced by the significantly transformed connection modes of Ag–Ag interactions in 1–3. As a result, the unique structural characteristics of 2, especially containing the Ag–Ag–Ag bonds, endow 2 with intact multinuclear reaction pathways and well-defined multinuclear platforms that can execute tandem acylation–Nazarov cyclization reaction through the cooperative effect of Ag–Ag–Ag interactions during the catalytic process.
Co-reporter:Xiao Han, Weixiang Gong, Yue Tong, Donghui Wei, Yanyan Wang, Jie Ding, Hongwei Hou, Yinglin Song
Dyes and Pigments 2017 Volume 137() pp:135-142
Publication Date(Web):February 2017
DOI:10.1016/j.dyepig.2016.10.005
•Benzothiadiazole-pyridine compounds were directly synthesized via a modified amination route.•They show the attracting modulation of optical and nonlinear optical (NLO) performances by molecular polarity feature.•Enhanced NLO molecular capability was connected with the quasi-D-A organic structure.•The switch-on of NLO refraction signaling from negative to positive, was triggered by the external Fe3+ ion.In this work, two new benzothiadiazole (BTD)-based compounds 1 and 2 were elaborately designed and synthesized, to explore the modulation on the interesting optical properties. Briefly, bipyridine-substituted compound 1 was synthesized via a modified Buchwald-Hartwig amination reaction with relatively high yield, and then derivative 2 was prepared by a following dehydrogenation reaction. The result in steady-state spectroscopic analysis and DFT/TDDFT calculation suggest the readily polarized nature of 1. In contrast, the readily polarized nature was declined in π-conjugated molecule 2, indicating the blue-shifted absorption and emission. Interestingly, negative cubic nonlinear refraction behavior in 1 is greater than that in π-conjugated system 2. Furthermore, in case 1 or 2, the photophycal property was considerably influenced by the external transition metal ion (M = Ag+, Cu2+ or Fe3+). Especially, because of the existence of external Fe3+ in case 1, initially negative nonlinear refraction signal became a positive one. Such exciting result is quietly useful for the design and synthesis of new functional BTD-based dye material.Bipyridine-substituted compound 1 was successfully synthesized via the modified Buchwald-Hartwig amination route with relatively high yield in relatively short reaction time. The relatively rigid derivative 2 was subsequently prepared by the simple dehydrogenation. Herein, two new BTD-pyridine compounds 1 and 2 show the attracting modulation of optical capability by the change of molecular polarity feature. In comparison with 1, polarized nature was declined in dehydrogenated 2, indicating the blue-shifted absorption and emission as well as weakened negative cubic nonlinear refraction.
Co-reporter:Haijuan Du, Yaru Li, Manman Xu, Yunyin Niu, Hongwei Hou
Journal of Molecular Structure 2017 Volume 1133() pp:101-110
Publication Date(Web):5 April 2017
DOI:10.1016/j.molstruc.2016.11.092
•Three new extended supramolecular structures have been prepared.•They exhibit diverse structures and semiconducting properties.•The optical and electrical properties were also investigated.Construction of viologen cation salts of d10 metal halide anions (inorganic-organic hybrid materials) with semiconducting properties via supramolecular design and aggregate enable the hybrid materials multifunctionality. Our interest focused on the use of the viologen derivatives as the building units because they were redox-active units and more suited to yield new generation of multifunctional networks. In the present investigation, three new inorganic-organic hybrid semiconductors {[bbpyb]·[AgBr3]}n (1) [1, 3-PMBP][Zn2Cl5.1Br0.9] (2) and [1, 3-PMBP][Zn2Br6] (3) (bbpyb = 1,1″-(1,4-butanediyl)bis[4,4′-bipyridinium]bis[bromide], 1,3-PMBP = 1,1″-[1,3-phenylene-bis(methylene)]bis-4,4′-bipyridinium-bisbromide) were synthesized. More importantly, great efforts were devoted to investigate their properties, such as optical and electrical properties. 1–3 exhibited photochromism, which can be ascribed to the intermolecular charge transfer to yield radicals. Fabricating the appropriate inorganic and organic units controllably within photosensitive materials at a molecular level is critical for the development of new photochromic inorganic-organic hybrids.
Co-reporter:Honghong Li;Yanbing Han;Zhichao Shao;Na Li;Chao Huang;Hongwei Hou
Dalton Transactions 2017 vol. 46(Issue 36) pp:12201-12208
Publication Date(Web):2017/09/19
DOI:10.1039/C7DT02590D
Two novel Eu metal–organic frameworks (MOFs), namely {[Eu2(pdba)3(H2O)3]·2H2O}n (1) and {[Eu3(pdba)4(H2O)4]·5H2O}n (2), were prepared with 4′-(1H-pyrazol-3-yl)-[1,1′-biphenyl]-3,5-dicarboxylic acid (H2pdba) under hydrothermal conditions. MOF 1 exhibits a 3D supramolecular structure assembled from the π⋯π interactions between the benzene rings of the ligands, whereas 2 comprises a 3D structure through coordination connection between nitrogen atom and Eu3+. It is worth noting that the two MOFs showed good luminescence performance and high-sensitivity fluorescence quenching behavior toward Fe3+ (Cr3+) and nitrobenzene. Furthermore, the experimental results for stability in water and cycle test show that these two MOFs can be used as potential fluorescent probes.
Co-reporter:Xiao Han, Zhiru Wang, Qing Cheng, Xiangru Meng, Donghui Wei, Yichao Zheng, Jie Ding, Hongwei Hou
Dyes and Pigments 2017 Volume 145(Volume 145) pp:
Publication Date(Web):1 October 2017
DOI:10.1016/j.dyepig.2017.06.039
•Two new benzothiadiazole-pyridine compounds were pH-sensitive in broad ranges (2–12).•In live cell imaging experiment, unique “turn-on” fluorescence response to increased pH was firstly observed.•The unique performance was dependent on mitochondrial function under different physiological pH conditions.•The first mitochondria-dependent benzothiadiazole-pyridine probe for cellular pH imaging in quantitative mode.In this work, we reported two new pH-sensitive benzothiadiazole-pyridine compounds 1 and 2, which distinctly showed the red-shifted absorption and “turn-off” fluorescence responses to increased pH in a broad range (pH = 2–12). Because of excllent mitochondria-immobilized preformance, suitable fluorescence detection window and linear response behavior in the range of pH = 5–8, compound 1 was suitable to explore as a imaging detector of intracelluar pH in live cell. More intereastingly, different from “turn-off” fluorescence response to increased pH in buffer solution, probe 1 displayed a “turn-on” fluorescence in live cell imaging experiment. This opposite performance between buffer solution and live cell are so unique that no such literature has been ever mentioned in our best knowledge. The further study revealed that this unique performance was dependent on the mitochondrial function under different physiological pH conditions. Herein, on the basis of special “turn-on” fluorescence response, intracellular pH was successfully imaged in a quantitatively ratiometric method by using 1 in conjunction with MitoTracker Red (MTR).In this paper, we reported the first example for quantitatively intracellular pH probe dependent on mitochondrial function under different physiological pH conditions.Download high-res image (287KB)Download full-size image
Co-reporter:Yuanyuan Li;Kai Li;Lili Wang;Yanling He;Juan He;Hongwei Hou;Ben Zhong Tang
Journal of Materials Chemistry C 2017 vol. 5(Issue 30) pp:7553-7560
Publication Date(Web):2017/08/03
DOI:10.1039/C7TC02437A
Fluoran dyes have been widely used as chromogenic reagents in piezochromic and thermochromic materials due to their intrinsic halochromic properties. However, reports on fluoran-based photochromic materials are still rare. In this work, a series of fluoran salicylaldehyde hydrazone Zn(II) complexes (1-Zn, 2-Zn and 3-Zn) were facilely prepared. The complexes exhibited excellent reversible photochromism with remarkable fatigue resistance both in solution and in a solid matrix. Due to the multiple colors of the fluoran parts, these complexes exhibited different colors after UV light irradiation. Particularly, a black color was obtained for 3-Zn, which is relatively infrequent because black photochromism systems are still very uncommon. The photochromic mechanism was proposed, where the tautomerism from the enol form to the keto form in the salicylaldehyde hydrazone moiety was induced by UV light irradiation, accompanied by a spirolactam ring-opening reaction and yielding colored products. A smaller group adjacent to the spirolactam ring was favorable for the stability of the colored products. The influences of different metal ions and solvents on the photochromism of these complexes were also studied. Moreover, patterns were successfully visualized in thin layer silica gel that was impregnated with the complexes after UV light irradiation, which suggested that they can be promising candidates for photo-patterning.
Co-reporter:Caixia Yu;Zhichao Shao;Hongwei Hou
Chemical Science (2010-Present) 2017 vol. 8(Issue 11) pp:7611-7619
Publication Date(Web):2017/10/23
DOI:10.1039/C7SC03308G
Heavy metal ions are highly toxic and widely spread as environmental pollutants. New strategies are being developed to efficiently remove these toxic ions. Herein, we use the intrinsic advantages of metal–organic frameworks (MOFs) and develop a porous Zn(II)-based MOF decorated with O− groups for the removal of Pb2+. Benefiting from its multiple porosity, sufficient adsorption sites and strong affinity, the activated MOF material exhibits an ultrahigh Pb2+ uptake capacity (616.64 mg g−1), surpassing all those of reported MOF adsorbents. Moreover, it can selectively capture Pb2+ with high efficiency (>99.27%) against background ions. Even in the presence of a high concentration of competitive ions, such as Ca2+ or Mg2+, effective removal (>99.21%) can also be achieved in a short time. The excellent removal performance demonstrates the strong electrostatic attraction and coordination interaction between the highly accessible O− groups and Pb2+. The possible adsorption mechanism was systematically verified by zeta potential, FT-IR and XPS studies. Our work reveals the enormous potential of functionalized MOFs as an appealing platform to construct sorbent materials.
Co-reporter:Kai Li;Yuanyuan Liu;Yuanyuan Li;Qi Feng;Hongwei Hou;Ben Zhong Tang
Chemical Science (2010-Present) 2017 vol. 8(Issue 10) pp:7258-7267
Publication Date(Web):2017/09/25
DOI:10.1039/C7SC03076B
Aggregation-induced emission luminogens (AIEgens) have attracted extensive interest for their outstanding luminescence properties in the aggregated state and even in the solid state. In this work, we developed a series of novel AIEgens based on 2,5-bis(4-alkoxycarbonylphenyl)-1,4-diaryl-1,4-dihydropyrrolo[3,2-b]pyrrole (AAPP). The AIEgens can be facilely synthesized through a single-step reaction under mild conditions with satisfactory yields. Interestingly, AAPP was found to have multiple luminous mechanisms that result in variable fluorescence properties. The propeller-like structure of AAPP enables a restricted intramolecular rotation (RIR) process which significantly enhances its fluorescence in the aggregated state (i.e. AIE fluorescence). In addition, there is a donor–acceptor interaction between the heterocycle center and the alkoxycarbonyl units in AAPP which allows a typical twisted intramolecular charge transfer (TICT) process in the dispersed state, resulting in strong fluorescence emissions in non-polar or low-polarity solvents but fluorescence quenching in high-polarity solvents. Due to the tunable RIR and TICT processes and the multiple fluorescence, AAPP compounds exhibit multifunctional applications: (1) as a reversible fluorescent thermometer, AAPP exhibited excellent fatigue resistance. There was a good linear relationship between its fluorescence intensity and temperature from 10 °C to 60 °C. (2) The desethyl AAPP derivative (CAPP) was successfully applied in the detection of Cd(II) in aqueous solution at neutral pH, and showed a 500-fold fluorescence “turn-on” response to Cd(II) with good selectivity.
Co-reporter:Xiao Han;Qing Cheng;Xiangru Meng;Zhichao Shao;Ke Ma;Donghui Wei;Jie Ding;Hongwei Hou
Chemical Communications 2017 vol. 53(Issue 74) pp:10314-10317
Publication Date(Web):2017/09/14
DOI:10.1039/C7CC06125K
The first example of micro-adjustments of a metal organic framework (MOF) structure was observed in a new Zn(II) MOF (Zn-BTDC-M1) derived from a benzothiadiazole-4,7-dicarboxylic acid (H2BTDC) ligand using a light-driven decarboxylation process. Interestingly, such decarboxylation occurs at the non-chelated wing of the ligand, which induced a change in the capability of the MOF for physical N2 adsorption and chemical NH3 gas adsorption.
Co-reporter:Lili Wang;Yuanyuan Li;Xuejiao You;Kui Xu;Qi Feng;Jinmin Wang;Yuanyuan Liu;Kai Li;Hongwei Hou
Journal of Materials Chemistry C 2017 vol. 5(Issue 1) pp:65-72
Publication Date(Web):2016/12/22
DOI:10.1039/C6TC03791G
Luminescent molecules with photochromic properties show strong potential in molecular switches, molecular logic gates, photo-controllable materials, bio-imaging, anti-counterfeiting, photo-patterning, etc. However, research is still scarce in such molecules exhibiting reversible photo-controllable color and fluorescence changes in solid states, which is due to the aggregation-caused quenching (ACQ) effect of most luminogens. In this work, a reversible photochromic molecule (1) with aggregation-induced emission (AIE) properties was developed. Compound 1 exhibits typical AIE properties as a result of restricted intramolecular rotation (RIR) and excited-state intramolecular proton transfer (ESIPT) processes. As a photochromic molecule, compound 1 shows reversible color and fluorescence changes upon UV light irradiation with good fatigue resistance. More importantly, the conversion rate from its irradiated form to its initial form is controllable by temperature and long wavelength light irradiation, which makes it suitable for photo-patterning materials with erasable properties.
Co-reporter:Qing Cheng, Xiao Han, Yue Tong, Chao Huang, Jie Ding, and Hongwei Hou
Inorganic Chemistry 2017 Volume 56(Issue 3) pp:
Publication Date(Web):January 20, 2017
DOI:10.1021/acs.inorgchem.6b02863
On the basis of the same benzothiadiazole (BTD) ligand 2,1,3-benzothiadiazole-4,7-dicarboxylic acid (H2L), two new isomers of three-dimensional (3D) BTD-derived Cd(II) metal–organic frameworks 1-2 {[S@Cd6L6]·xH2O}n were obtained by the different solvothermal reactions, which were structurally similar. Surprisingly, structural analyses reveal that in 1 or 2, one free sulfur atom was fixed in a Cd(II) cluster cage by strong intermolecular interaction to form the secondary building unit (SBU) S@Cd6. Each SBU S@Cd6 is connected by six L2– ligands and further extended into the 3D porous framework. In this work, the BTD antidimmer was evidenced by structural analysis and photophysical study. Furthermore, either 1 or 2 showed the uncommon dual emission, while only one emission was observed in the solution of ligand H2L. The dual-emission mechanism was also realized by the structural analysis and photophysical study. Interestingly, although there is slight difference in structure (regular octahedral cage in 1 and slightly distorted octahedral cage in 2), the changes in N2 adsorption capability and photophysical performance between 1 and 2 are obvious, where 2 shows smaller Brunauer–Emmett–Teller surface area, broader absorption of antidimmer, and longer dual-emission lifetimes. Interestingly, either 1 or 2, the dual emission was clearly red-shifted by increasing the solvent polarity or the acidity of ambience, respectively.
Co-reporter:Huarui Wang, Wei Meng, Jie Wu, Jie Ding, Hongwei Hou, Yaoting Fan
Coordination Chemistry Reviews 2016 Volume 307(Part 2) pp:130-146
Publication Date(Web):15 January 2016
DOI:10.1016/j.ccr.2015.05.009
•Detailed study on crystalline central-metal reform is benefit to modify MOF material.•SCO induced by host-guest interactions in MOFs is reviewed.•It shows a way to get functional MOFs by altering node metal's valence in SCSC mode.•Crystalline divalent and monovalent central-metal exchanges are displayed.•Particular attention is paid to see the exchange mechanism on a case-by-case basis.Recently, there has been considerable interest in the transformation of metal nodes in metal-organic frameworks (MOFs) because this transformation can yield favorable changes in their chemical or physical properties. In this review, we provided an overview of crystalline central-metal transformation in MOFs, including central-metal spin-state transformation, central-metal oxidation-state transformation, and central-metal exchange in a single-crystal-to-single-crystal manner. Investigations of this concept suggest that crystalline central-metal transformation will play an emerging role in the exploration of novel MOFs for use in further applications in the near future.Overview of the recent development of crystalline central-metal transformation in MOFs, including central-metal spin-state transformation, oxidation-state transformation, and exchange. The rapid increase in investigations in this area suggest that it will play an emerging role in the exploration of novel MOFs for use in future applications.
Co-reporter:Qi Feng, Yuanyuan Li, Lili Wang, Chen Li, Jinmin Wang, Yuanyuan Liu, Kai Li and Hongwei Hou
Chemical Communications 2016 vol. 52(Issue 15) pp:3123-3126
Publication Date(Web):18 Jan 2016
DOI:10.1039/C5CC10423H
A series of 4-N,N-dimethylaminoaniline salicylaldehyde Schiff-base derivatives (DAS) were facilely prepared. They exhibit typical AIE properties with various fluorescence emissions and high fluorescence quantum yields in an aggregated state. DAS exhibit unique pH-dependent optical properties, which indicated their potential applications in pH sensing.
Co-reporter:Li’an Guo, Chao Huang, Lu Liu, Zhichao Shao, Yue Tong, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2016 Volume 16(Issue 9) pp:4926
Publication Date(Web):August 3, 2016
DOI:10.1021/acs.cgd.6b00494
We have obtained a suite of two-dimensional layered isostructural coordination polymers [M(pypa)2(H2O)2]n (M = Mn (1), Co (2), Ni (3), Cu (4), respectively), Hpypa = 1H-[3-(4-pyridy)pyrazole]propionic acid), and used them in catalyzing the homocoupling of aromatic halides. 3 and 4 exhibit preeminent catalytic performance on the homocoupling of aryl bromide or aryl iodide without byproducts, while 2 only promoted the homocoupling of aryl iodide. But 1 showed no catalytic activities for all tested aromatic halides. Subsequently, density functional theory was performed for the balanced geometry frameworks, net charges of atoms, and energy of frontier molecule orbits. By using this method we determined that the catalytic performance was influenced by central metal ions. For further improving the catalytic performance, polyvinylpyrrolidone or polyethylene glycol 20000 (PEG 20000) was used as surfactants to synthesize the microscales of 3’s (3a and 3b). 3a and 3b showed more preeminent catalytic activity than 3.
Co-reporter:Haijuan Du, Wenli Zhang, Chaohai Wang, Yunyin Niu and Hongwei Hou
Dalton Transactions 2016 vol. 45(Issue 6) pp:2624-2628
Publication Date(Web):18 Dec 2015
DOI:10.1039/C5DT04508H
A new nanocrystalline inorganic–organic hybrid semiconductor [(BV)2(Ag5Br9)]n (1) with an intriguing windmill-like 1-D [Ag5Br9]nn− polymeric chain was assembled. Great efforts were devoted to investigate its semiconducting properties and applications, such as photoluminescence, emission decay lifetime, waste water purification, electrochemistry behavior and dielectric properties.
Co-reporter:Huarui Wang, Chao Huang, Yanbing Han, Zhichao Shao, Hongwei Hou and Yaoting Fan
Dalton Transactions 2016 vol. 45(Issue 18) pp:7776-7785
Publication Date(Web):29 Mar 2016
DOI:10.1039/C6DT00726K
The rigid and planar tetracarboxylic acid 5,5′-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid (H4L), incorporating a triazole group, has been used with no or different pyridine-based linkers to construct a family of d10 coordination polymers, namely, {[H2N(CH3)2]3[Cd3(L)2(HCOO)]}n (1), {[Cd2(L)(py)6]·H2O}n (2), {[H2N(CH3)2] [Cd2(L)(HCOO)(H2O)4]}n (3), {[Zn(H2L)]·H2O}n (4), and {[Zn(H2L)(4,4′-bipy)0.5]·C2H5OH·H2O}n (5) (py = pyridine, 4,4′-bipy = 4,4′-bipyridine). 1 constructs a 3D porous network containing two kinds of channels: one is filled with coordinated HCOO− anions, and the other with [H2N(CH3)2]+ cations. The framework of 1 can be described as a rare (5,6,7)-connected net with the Schläfli symbol of (412·5·62)(45·53·62)2(48·53·68·82)2. The Cd(II) ions in 2 are connected through the carboxylate ligands to form a 2D layer, with aperture dimensions of ∼15.1 Å × 16.2 Å. The network of 3 features a 3D (3,4)-connected (6·8·10)2(6·83·102) topology. A 3D network with the (42·6·83) topology of 4 possesses an open 1D channel with the free volume of 29.2%. 5 is a 2D layer structure with the (42·63·8)(42·6) topology. The fluorescence lifetime τ values of 1–5 are on the nanosecond timescale at room temperature. In particular, central-metal exchange in 2 leads to a series of isostructural M(II)–Cd frameworks [M = Cu (2a), Co (2b), Ni (2c)] showing improved catalytic activity for the synthesis of 1,4,5,6-tetrahydropyrimidine derivatives. Based on this, a plausible mechanism for the catalytic reaction has been proposed and the reactivity–structure relationship has been further clarified.
Co-reporter:Yue Tong, Xiao Han, Chao Huang, Zhichao Shao, Li'an Guo, Yazhen Wang, Jie Ding and Hongwei Hou
Dalton Transactions 2016 vol. 45(Issue 9) pp:3702-3705
Publication Date(Web):08 Feb 2016
DOI:10.1039/C6DT00067C
Several new isostructural lanthanide metal–organic frameworks {[Ln3(L)4(OH)(H2O)2]·DMAC}n (Ln = Tb (1), Gd (2), Eu (3), Gd0.81Tb0.10Eu0.09 (4) and Gd0.75Tb0.18Eu0.07 (5)) were designed and prepared. Excitingly, samples 1, 3, 4 and 5 showed reversible Al3+-induced chromaticity switching as well as reversible Fe3+-induced emission switching.
Co-reporter:Huarui Wang, Jianhua Qin, Chao Huang, Yanbing Han, Wenjuan Xu and Hongwei Hou
Dalton Transactions 2016 vol. 45(Issue 32) pp:12710-12716
Publication Date(Web):11 Jul 2016
DOI:10.1039/C6DT02321E
Eleven water-stable isostructural mono/bimetallic lanthanide coordination polymers (Ln-CPs) {[EuxTb1−x (HL)(H2O)3]·H2O}n (x = 1.0 (1), 0.9 (3), 0.8 (4), 0.7 (5), 0.6 (6), 0.4 (7), 0.3 (8), 0.2 (9), 0.1 (10), 0.05 (11), 0 (2), H4L = 5,5′-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid) with uncoordinated Lewis basic triazole sites within the pores were prepared. The Ln-CPs represented by 1 showed a rapid and drastic emission quenching induced by external Fe3+ and Cr3+ cations and CrO42− and CO32− anions in aqueous solution. In addition, because of the comparable emission intensities of Eu3+ and Tb3+ ions, bimetallic CP 8 can be used as a ratiometric luminescent sensor for organic solvent molecules. Moreover, the luminescent color of the 8 sensor in pyridine and in other guest solvents undergoes obvious changes that can be clearly distinguished by the naked eye.
Co-reporter:Chaohai Wang, Haijuan Du, Yabin Lu, Manman Xu, Benlai Wu, Yunyin Niu, and Hongwei Hou
Crystal Growth & Design 2016 Volume 16(Issue 5) pp:2487
Publication Date(Web):April 4, 2016
DOI:10.1021/acs.cgd.6b00301
A series of organic–inorganic polypseudorotaxanes based on Cux(SCN)y polyanionic ring and bis(3,5-lutidine)alkyl dication threads are reported. This kind of interesting bis(pyridinium)alkyl template may facilitate the formation of 2D polypseudorotaxane. All these complexes exhibit excellent photochemical properties.
Co-reporter:Hui-Qin Zheng, Xiao-Bo Wang, Ji-Yong Hu, Jin-An Zhao, Chen-Xia Du, Yao-Ting Fan, Hong-Wei Hou
Solar Energy 2016 Volume 132() pp:373-385
Publication Date(Web):July 2016
DOI:10.1016/j.solener.2016.03.010
•Four new bionic photocatalysts (1–4) with [2Fe2S] model complexes were reported.•H2 evolution of 1–4 was evaluated, the max H2 yield reached 52.9 ± 1.6 TON (vs. 4).•Inactivity of system was mainly due to photo-degradation of EBS2− and catalyst (1–4).•Reduced FeIFe0 species could be formed by ET from 1*EBS2− to FeIFeI.•The effect of [2Fe2S] complexes’ structure on H2 production mechanism was discussed.Four novel [2Fe2S] model complexes (1–4) had been synthesized and characterized by IR, 1H NMR, elemental analysis and single crystal X-ray crystallography (for 2). The key parameters affecting H2 evolution of title compounds (1–4) were optimized by constructing homogeneous photo-catalytic system consisting of title compounds (1–4) as catalyst, erythrosin B sodium salt (EBS2−) as photo-sensitizer (PS) and triethylamine (TEA) as sacrificial reagent in CH3CN/H2O solution under the irradiation of visible light. The maximum H2 evolution was separately 211.4 ± 6.5 μmol (52.9 ± 1.6 TON vs. 4), 199.4 ± 13.5 μmol (49.9 ± 3.4 TON vs. 1), 124.8 ± 7.6 μmol (31.2 ± 1.9 TON vs. 3) and 34.9 ± 6.9 μmol (8.7 ± 1.7 TON vs. 2) under the optimal conditions with catalyst of 2 × 10−4 mol·L−1, EBS2− of 4 × 10−4 mol·L−1, TEA of 10% (v/v) and pH 12 in CH3CN/H2O (1/1, v/v) solution. Furthermore, the structural effect and mechanism of electron transfer in the present system was carefully discussed by fluorescence spectra and cyclic voltammetry (CV) measurements.We have constructed a homogeneous photo-catalytic system using [2Fe2S] model complexes 1–4 as biomimetic photo-catalysts, EBS2− as PS and TEA as sacrificial reagent in CH3CN/H2O (v/v, 1/1) solution under the visible light irradiation. The H2 evolution performance and mechanism of target complexes 1–4 were evaluated. The result suggested that the different structures of [2Fe2S] simulate complexes affect on H2 evolution performance and mechanism, the maximum H2 evolution was 211.4 ± 6.5 μmol (52.9 ± 1.6 TON vs. 4). The H2 generation mechanism might be able to firstly form an intermediate Fe0FeI by electron transferring from 1*EBS2− to [2Fe2S] center, and then underwent an ECEC (for 1, 2 and 4) or EECC (for 3) process to form the important H2–Fe2S2 (η2-H2–FeIIFeI) species of H2 production. The result indicated the target complexes are potential candidates as photo-catalysts for H2 generation.
Co-reporter:Jianhua Qin, Bing Ma, Xiao-Fei Liu, Hong-Lin Lu, Xi-Yan Dong, Shuang-Quan Zang and Hongwei Hou
Journal of Materials Chemistry A 2015 vol. 3(Issue 24) pp:12690-12697
Publication Date(Web):2015/05/06
DOI:10.1039/C5TA00322A
A water-stable fluorescent microporous metal–organic framework (MOF), [Tb(L)(OH)]·x(solv) (1), has been designed and successfully synthesized under a combination of hydro/solvothermal and ionothermal conditions (H2L = 5-(4-carboxyphenyl)pyridine-2-carboxylate). The crystal structure reveals that complex 1 consists of cubane-shaped tetranuclear terbium building units, which are further bridged by the multicarboxylate ligands to give a (3,12)-connected topology with the point symbol (420·628·818)(43)4. More importantly, the excellent hydrolytic stability allows it to be used in an aquatic system, which is highly desirable for practical applications. Activated 1 shows high selectivity and sensitivity towards nitroaromatic explosives in both aqueous and vapor phases. The sizes of the pore windows (11.2 × 11.2 Å2) in 1, which are larger than the sizes of the selected nitroaromatics, could permit easy diffusion of analytes inside the channel, keeping the electron rich framework and electron deficient analytes in close proximity.
Co-reporter:Chao Huang, Jie Wu, Chuanjun Song, Ran Ding, Yan Qiao, Hongwei Hou, Junbiao Chang and Yaoting Fan
Chemical Communications 2015 vol. 51(Issue 51) pp:10353-10356
Publication Date(Web):07 May 2015
DOI:10.1039/C5CC02432C
Upon single-crystal-to-single-crystal (SCSC) oxidation/reduction, reversible structural transformations take place between the anionic porous zeolite-like CuI framework and a topologically equivalent neutral CuICuII mixed-valent framework. The unique conversion behavior of the CuI framework endowed it as a redox-switchable catalyst for the direct arylation of heterocycle C–H bonds.
Co-reporter:Ming Li, Yi Yao, Jie Ding, Lu Liu, Jianhua Qin, Yaopeng Zhao, Hongwei Hou, and Yaoting Fan
Inorganic Chemistry 2015 Volume 54(Issue 4) pp:1346-1353
Publication Date(Web):January 14, 2015
DOI:10.1021/ic502219y
To explore new 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-derived metal–organic frameworks (MOFs), we employed 2,6-dicarboxyl-1,3,5,7-tetramethyl-8-phenyl-4,4-difluoroboradiazaindacene (H2L) as a ligand to successfully synthesize five coordination polymers, namely, {[Zn2(L)2(bpp)]·2H2O·2EtOH}n (1), {[Cd2(L)2(bpp)]·2H2O·EtOH}n (2), {[Cd2(L)(bpe)3(NO3)2]·2H2O·DMF·EtOH}n (3), {[Cd(L)(bpe)0.5(DMF)(H2O)]}n (4), and {[Cd(L)(bpe)0.5]·1.5H2O·DMF}n (5) (bpp = 1,3-bi(4-pyridyl)propane, bpe = 1,2-bi(4-pyridyl)ethane). Except for two 2D-layer coordination polymers 3 and 4, the rest samples exhibit 3D metal–organic frameworks with certain pore sizes, especially MOFs 1 and 5. Spectroscopic and crystallographic investigations demonstrate that the absorption and emission energies of the BODIPY chromophores are sensitive to the coordination modes. Moreover, in case 2, the transition metal centers coordinated with the dicarboxylate ligands L2– are capable of forming the two BODIPY units in coplanar arrangements (θ = 37.9°), simultaneously suppressing the uncommon J-dimer absorption band centered at 705 nm with a long tail into the near-infrared region at room temperature. On the other hand, in comparison with the ligand H2L, the emission of monomer-like BODIPY in case 3 is enhanced in the solid state by a considerably long distance between the parallel BODIPY planes (about 14.0 Å).
Co-reporter:Ran Ding, Chao Huang, Jingjing Lu, Junning Wang, Chuanjun Song, Jie Wu, Hongwei Hou, and Yaoting Fan
Inorganic Chemistry 2015 Volume 54(Issue 4) pp:1405-1413
Publication Date(Web):January 28, 2015
DOI:10.1021/ic502369y
Solvent templates induced Co-based metal–organic materials; conformational isomers {[Co2(pdpa)(CH3CN)(H2O)3]·CH3OH·H2O}n (1) and {[Co2(pdpa)(CH3CN)(H2O)3]}n (2) and {[Co5(pdpa)2(μ3-OH)2(H2O)6]·2H2O}n (3) [H4pdpa = 5,5′-(pentane-1,2-diyl)-bis(oxy)diisophthalic acid] were synthesized under the same solvothermal conditions except with different concentrations of cyclic ethers (1,4-dioxane or tetrahydrofuran) as structure-directing agents. Structural transformations from a three-dimensional (3D) framework of 1 containing channels with dimensions of ∼6 Å × 6 Å to a two-dimensional layer structure of 2 consisting of large open channels with a size of ∼15 Å × 8 Å and then to a 3D nonporous framework of 3, resulting from the different concentrations of cyclic ethers, were observed. The anion−π interactions between electron-efficient oxygen atoms of cyclic ethers and electron-deficient dicarboxylic acid aromatic cores in H4pdpa imported into the synthetic process accounted for the conformational change of the ligand H4pdpa and the following structural variations. A systematic investigation was conducted to explore how different concentrations of structure-directing agents affected the frameworks of resultant metal–organic frameworks. Furthermore, 1–3 were shown to be available heterogeneous catalysts for the synthesis of 2-imidazoline and 1,4,5,6-tetrahydropyrimidine derivatives by the cascade cycloaddition reactions of aromatic nitriles with diamines. The results showed that the catalytic activity of 2 was much higher than that of 1 and 3, because of its unique structural features, including accessible catalytic sites and suitable channel size and shape. In addition, a plausible mechanism for these catalytic reactions was proposed, and the reactivity–structure relationship was further clarified.
Co-reporter:Jian-Hua Qin, Hua-Rui Wang, Qi Pan, Shuang-Quan Zang, Hongwei Hou and Yaoting Fan
Dalton Transactions 2015 vol. 44(Issue 40) pp:17639-17651
Publication Date(Web):08 Sep 2015
DOI:10.1039/C5DT03026A
Seven Mn(II) coordination polymers, namely {[Mn2(ptptp)Cl2(H2O)3]·H2O}n (1), {[Mn(μ-ptptp)3]2[Mn3(μ3-Cl)]2}·2Cl·16H2O (2), {[Mn2(ptptp)(ip)2(H2O)3]·H2O}n (3), {[Mn2(ptptp)(5-CH3-ip)2(H2O)3]·H2O}n (4), {[Mn4(ptptp)(5-Br-ip)3(H2O)3]·4H2O}n (5), {[Mn2(ptptp)(Hbtc)(H2O)2]·2H2O}n (6) and {[Mn2(ptptp)(tdc)(H2O)2]·1.5H2O}n (7), have been prepared based on multidentate N-heterocyclic aromatic ligands and bridging carboxylate ligands (H2ptptp = 2-(5-{6-[5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl]pyridin-2-yl}-1H-1,2,4-triazol-3-yl)pyrazine; R-isophthalic acids, H2ip-R: R = –H (3), –CH3 (4), –Br (5); H3btc = trimesic acid (6); H2tdc = thiophene-2,5-dicarboxylic acid (7)), in order to further probe the multiple roles of [RMI]Br ionic liquids in the hydro/solvothermal synthesis (RMI = 1-alkyl-3-methylimidazolium, R = ethyl, or propyl, or butyl). The successful syntheses of complexes 2–6 suggest that in hydro/solvothermal synthesis the addition of a small amount of [RMI]Br plays a crucial role. Complex 1 exhibits single right-handed helices constructed by ptptp ligands and Mn(II) ions. Complex 2 possesses octanuclear helicate structures in which two propeller-shaped [Mn(μ-ptptp)3]4− units embrace two [Mn3(μ3-Cl)]5+ cluster cores inside. Complexes 3 and 4 are isostructural and display a 1D double chain formed by two kinds of pseudo meso-helices: (Mn-ptptp)n and (Mn-5-R-ip)n. Complex 5 has a 2D structure containing 1D Mn(II) ion chains formed through carboxylates and [ptptp]2−-N,N bridges. Complex 6 shows a 2D structure formed by a meso-helix (Mn-ptptp)n and the partly deprotonated Hbtc ligands. Complex 7 features a heterochiral [2 + 2] coaxially nested double-helical column formed by using the outer double-helices (Mn-ptptp)n as a template to encapsulate the inner double-helices (Mn-tdc)n with opposite orientation. All complexes were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, single-crystal X-ray crystallography and powder X-ray diffraction. The magnetic properties of 1–7 were also investigated.
Co-reporter:Lu Liu, Chao Huang, Xiaonan Xue, Ming Li, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2015 Volume 15(Issue 9) pp:4507-4517
Publication Date(Web):August 4, 2015
DOI:10.1021/acs.cgd.5b00757
To seek the effect that condition of the complexes has on the manufacture of the biaryl compounds, seven Ni(II) complexes, namely, {[Ni(L)0.5(bpa)(H2O)]·2H2O}n (1), {[Ni2(L)(dpp)2(H2O)]·4H2O}n (2), {[Ni(L)0.5(pbmb)(H2O)]·H2O}n (3), {[Ni2(L)(bmp)2(H2O)]·7H2O}n (4), {[Ni(L)0.5(pbib)1.5]·2H2O}n (5), {[Ni2(L)(pbib)1.5]·3H2O}n (6), and [Ni(L)0.5(beb)2(H2O)]n (7) (bpa = 1,2-bis(4-pyridyl)ethane, dpp = 1,3-di(4-pyridyl)propane, pbmb = 1,1′-(1,3-propane)bis(2-methylbenzimidazole), bmp = 1,5-bis(2-methylbenzimidazol) pentane, pbib = 1,4-bis(imidazol-1-ylmethyl)benzene, beb = 1,4-bis(2-ethylbenzimidazol-1-ylmethyl)benzene), have been gained through hydro(solvo)thermal reactions of 5,5′-(hexane-1,6-diyl)-bis(oxy)diisophthalic acid ligand (H4L) with Ni(II) metal ions under the regulation and control of six N-donor ligands. 3-fold interpenetrating complex 1 belongs to a (4,4)-connected 3D bbf net with a vertex symbol of (64·82)(66) topology. 3-fold interpenetrating complex 2 presents a (4,4,4)-connected 3D bbf net with a Schläfli symbol of (66)2(64·82) topology. 3 features a (3,4)-connected 3,4L13 topology with a Schläfli symbol of (4·62)(42·62·82) topology. 4 possesses a (4,4,4)-connected mog Moganite 3D network fabric, and the vertex symbol is (4·64·8)2(42·62·82). 5 takes on a (4,5)-connected architecture, and the point symbol is (4·69)(42·66·82). 6 is a (4,7)-connected framework, and the Schläfli symbol is (45·5)(47·53·611). 7 has a (4,4)-connected 4,4L28 topology, and the point (Schläfli) symbol is (42·64)(4·64·8). A systematic structural comparison of 1–7 signifies that their frameworks can be regulated through varied conformations of the flexible H4L ligand and diverse N-donor ligands. Between the proximal Ni(II) ions, the variable-temperature (2–300 K) magnetic susceptibilities of 6 display overall weak antiferromagnetic coupling. In the complexes-catalyzed homocoupling reaction of iodobenzene, 3, 5, 6, and 7 have been verified to be effectual catalysts for the synthesis of the biaryl compounds.
Co-reporter:Lin Zhang, Lu Liu, Chao Huang, Xiao Han, Li’an Guo, Hong Xu, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2015 Volume 15(Issue 7) pp:3426
Publication Date(Web):June 15, 2015
DOI:10.1021/acs.cgd.5b00504
By the solvothermal reactions of a [1,1′:3′,1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid (H4tpta) with transition metal ions, three novel polymeric complexes, namely {[Ni2(tpta)(H2O)3]·H2O}n (1), {[Co4(tpta)2(4,4′-bpy)(H2O)3]·3H2O}n (2), and {[Mn2(tpta)(H2O)2]·2H2O}n (3), have been isolated. The heterometallic clusters of these polymeric complexes are dimeric and tetrameric, respectively. 1 is composed of dimeric paddle wheel Ni(II) units to generate a 2D structure. In complexes 2 and 3, metal ions form tetrameric units that extend via all dimensions to give 3D structures with the Schläfli symbol of (43)(43)(46·618·84) and (46)(412·53·69·74), respectively. The results of variable temperature magnetization measurements (χmT-T and χm–1-T) show that complexes 1 and 2 display unusual ferromagnetic coupling via the M–O–C–O–M bridges, while complex 3 shows predominantly antiferromagnetic behavior. The M(H) curve of 1 does not saturate until the highest field of 80 kOe, indicating the significant magnetic anisotropy in this complex system, whereas the final saturation value of 2.79 Nβ for 2 manifests the existence of typically paramagnetic property and the absence of long-range magnetic ordering. The dynamic magnetization experiments have been also carried out to further explore the magnetic behaviors of 1 and 2. There are no frequency dependences in the dynamic magnetization experiments, suggesting the absence of slow magnetic relaxation of these two complexes.
Co-reporter:Lu Liu, Chao Huang, Lin Zhang, Ran Ding, Xiaonan Xue, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2015 Volume 15(Issue 6) pp:2712
Publication Date(Web):April 17, 2015
DOI:10.1021/acs.cgd.5b00016
To systematically explore the impact of coordination complexes on the synthesis of 2-imidazoline and 1,4,5,6-tetrahydropyrimidine derivatives, five Co(II)/Mn(II)/Cu(II) architectures, formulated as {[Co(L)0.5(H2O)2]·CH3OH·H2O}n (1), {[Co(L)0.5(pbib)]·4H2O}n (2), [Mn(L)0.5(Hatz)0.5(H2O)]n (3), {[Cu(L)0.5(phen)2][Cu(L)0.5(phen)2]·0.5L·5H2O}n (4), and {[Cu(L)0.5(2,2′-bpy)(H2O)]·H2O}n (5) (H4L = 5,5′-(hexane-1,6-diyl)-bis(oxy)diisophthalic acid, pbib = 1,4-bis(imidazol-1-ylmethyl)benzene, Hatz = 1H-1,2,4-triazol-3-amine, phen = 1,10-phenanthroline, 2,2′-bipy = 2,2′-bipyridine), have been designed and synthesized. 1 presents a (4,4)-connected 2D sql net with its point (Schläfli) symbol of (44·62)2, which is finally extended to a 3D supramolecular framework by π···π stacking interactions. 2 has a 3D (4,4)-connected new topology net with a point symbol of (86)2. 3 features a (4,4)-connected 3-fold interpenetrating 3D pts topology network with the Schläfli symbol (42·84)2. 4 possesses two binuclear molecules, and these adjacent binuclear units are further stretched to a 2D infinite packing structure through two distinct types of π···π stacking interactions. 5 is a 2D layer structure with the (8)(84·122) topology. The magnetic studies of 1 and 3 elucidate that both of them signify antiferromagnetic interactions. 4 and 5 have been justified to be available heterogeneous catalysts for the synthesis of 2-imidazoline and 1,4,5,6-tetrahydropyrimidine derivatives.
Co-reporter:Lina Zhang, Shuting Lu, Chao Zhang, Chenxia Du and Hongwei Hou
CrystEngComm 2015 vol. 17(Issue 4) pp:846-855
Publication Date(Web):24 Nov 2014
DOI:10.1039/C4CE02023E
Two novel Dy-based MOFs, namely, {[Dy2(PA)3(H2O)3(DMF)]·(DMF)2·(H2O)}n (1) and [Dy2(PA)3(H2O)2(DMF)2]·(DMF)3·(H2O)}n (2) (H2PA = pamoic acid), were solvothermally synthesized from the reaction of Dy(NO3)3 and H2PA at different pH values. Interestingly, both complexes can be obtained simultaneously within the pH range of 5.0–6.2, while higher pH values (6.2–7.0) promote the formation of compound 1 and lower pH values (2.0–5.0) tend to produce pure complex 2. Single-crystal X-ray diffraction studies indicate that 1 and 2 are both three-dimensional frameworks composed of dinuclear Dy(III) subunits featuring pcu networks with the point symbol of {412·63}. Significantly, their slight structure difference results in these two compounds showing completely different magnetic properties. Variable temperature magnetization measurements (χMT–T) demonstrate ferromagnetic interactions in compound 1, while possible antiferromagnetic interactions were observed in compound 2. Alternating current (ac) susceptibility measurements indicate that both the in-phase (χ′) and out-of-phase (χ′′) components showed frequency dependence in compound 1, suggesting that there is a slow relaxation behavior of the magnetization, which is typical of single-molecule magnets (SMMs), while no out-of-phase ac signal was noticed for 2. Furthermore, both 1 and 2 exhibit the characteristic luminescence of Dy3+ upon excitation at 365 nm, but with different intensities. The reasons for such magnetic and luminescence differences are discussed in detail.
Co-reporter:Zhichao Shao, Chao Huang, Xiao Han, Huarui Wang, Angran Li, Yanbing Han, Kai Li, Hongwei Hou and Yaoting Fan
Dalton Transactions 2015 vol. 44(Issue 28) pp:12832-12838
Publication Date(Web):29 May 2015
DOI:10.1039/C5DT01457C
A series of 2D layered isostructural coordination complexes {[M3(L)2(H2O)6]·H2O}n (M = Mn (1), Mn0.7Co0.3 (2), Mn0.5Co0.5 (3), Mn0.3Co0.7 (4), and Co (5), respectively, H3L = 1-aminobenzene-3,4,5-tricarboxylic acid) have been synthesized under hydrothermal conditions, and applied to catalyze the reaction of degenerating organic dyes under visible light irradiation. The photocatalytic results indicate that complex 5 exhibits good photocatalytic properties in the presence of H2O2, while 1 can restrain the photodegradation of organic dyes. Remarkably, when Mn ions are gradually replaced by Co ions in the complexes, the photocatalytic activities of 1–5 turn from inhibition to promotion, which is a controllable regulation of photocatalytic properties via changing metal ions. Moreover, by using novel magnetic analysis methods and diffuse-reflectance UV/Vis spectra analysis methods, we explain the influence of central metal ions on the photocatalytic performance.
Co-reporter:Lina Zhang, Chao Zhang, Bin Zhang, Chenxia Du and Hongwei Hou
CrystEngComm 2015 vol. 17(Issue 14) pp:2837-2846
Publication Date(Web):02 Mar 2015
DOI:10.1039/C5CE00263J
Two series of new lanthanide coordination polymers have been obtained by solvothermal reaction of Ln(NO3)3 and pamoic acid under different pH values. Both series of compounds show three-dimensional porous frameworks composed of dinuclear Ln(III) subunits. Series B demonstrates fascinating solvent-induced dynamic behaviors in an SCSC (single crystal to single crystal) manner. The capability of activated series B to absorb liquid acetone was investigated by means of 1H NMR spectroscopy, demonstrating the potential of Ln-MOFs as highly efficient and reusable liquid acetone sorbents. In addition, photoluminescence properties of Nd (3), Eu (5) and Yb (10) were measured and discussed. Lanthanide contraction effect also played a crucial role in the formation of each series of complexes. Analysis of the relations between the ionic radius (Ln3+) and the number of f electrons in these complexes indicates that lanthanide contraction effect in both series can be well described by the Raymond model.
Co-reporter:Jian-Hua Qin, Bing Ma, Xiao-Fei Liu, Hong-Lin Lu, Xi-Yan Dong, Shuang-Quan Zang and Hongwei Hou
Dalton Transactions 2015 vol. 44(Issue 33) pp:14594-14603
Publication Date(Web):01 Jul 2015
DOI:10.1039/C5DT02054A
Reactions of lanthanide nitrate, 1,3,5-benzenetrisbenzoic acid (H3BTB) and [RMI]Br ionic liquids (RMI = 1-alkyl-3-methylimidazolium; R = ethyl, propyl, butyl, amyl, or hexyl), gave rise to two novel lanthanide metal–organic frameworks (Ln-MOFs) [Ln(BTB)H2O], where Ln = Eu 1, Tb 2. In addition to helping solubilise the starting materials under the reaction conditions there is evidence that [RMI]Br itself can play a structure directing role and is intimately involved in template ordering in [Ln(BTB)H2O], even though neither the [RMI]+ cation nor the Br− anion is occluded into the ultimate structure. 1 and 2 are isostructural and consist of infinite rod-shaped lanthanide-carboxylate building units which are further bridged by trigonal-planar BTB ligands to give noninterpenetrated open 3D frameworks featuring a (6,6)-connected topology with the point symbol (44·67·84)(48·67). Importantly, the strong emission of 1 and 2 dispersed in water prompted us to explore their application for detection of different nitroaromatics in an aquatic system. 1 and 2 show similar selectivity and sensitivity towards the presence of trace amounts of nitroaromatic analytes in the aqueous phase, showing potential as explosive sensors.
Co-reporter:Haijuan Du, Chaohai Wang, Yao Li, Wenli Zhang, Manman Xu, Sumin Li, Yabin Lu, Yunyin Niu, Hongwei Hou
Microporous and Mesoporous Materials 2015 Volume 214() pp:136-142
Publication Date(Web):15 September 2015
DOI:10.1016/j.micromeso.2015.05.021
•An interesting BiI3 oligomeric structure was prepared through solvothermal route.•Compound 1 is a 2D supramolecular network with channels.•It can readily and quickly adsorb rhodamine B (RhB) and methylene blue.The solvothermal reaction of a mixture of bismuth iodide, flexible cationic compound 1,1″-(1,4-butanediyl)bis[4,4′-bipyridinium] bis[tetrafluoroborate] (bbpyf) and HI at the temperature of 110 °C resulted in a novel compound, namely [bbpy][Bi4I16] (1). The structure of compound 1 was explored with IR spectroscopy, thermal gravimetric analysis (TGA), PXRD, UV–vis diffuse reflectance spectra and single-crystal X-ray diffraction in the solid state. Compound 1 was a 2D supramolecular structure consisted of one linear cationic compound bbpy2+ and inorganic anion cluster [Bi4I16]2− and contained a channel of 11.214 × 9.727 Å via noncovalent interactions. In addition, the adsorption behavior of 1 was also investigated. And it could adsorb methylene blue (MB) and Rhodamine B (RhB) from waste water fast and effectively, highlighting its potential application for environmental issues.
Co-reporter:Huijun Li, Yuan Wang, Hongxin Cai, Zhouqing Xu, Lei Jia and Hongwei Hou
RSC Advances 2015 vol. 5(Issue 109) pp:89833-89838
Publication Date(Web):14 Oct 2015
DOI:10.1039/C5RA18219K
By treating FeSO4 or Mn(OAc)2 with 5′-(pyridin-2-yl)-2H,4′H-3,3′-bi(1,2,4-triazole) (H2pbt), three novel metallamacrocycle-based complexes [Fe(Hpbt)(C2O4)0.5]n (1), {[Fe(pbt)(H2O)]·2H2O}n (2), {[Mn(pbt)(H2O)]·2EtOH·0.5H2O}n (3) have been synthesized and characterized. In 1, the hexanuclear metallamacrocycle units are connected with each other resulting in the formation of two-dimensional frameworks. Octanuclear metallamacrocycle-based complexes 2 and 3 display three-dimensional porous frameworks. Interestingly, left- and right-handed helical chains present alternately along the crystallographic c axis in 2 and 3. Magnetic susceptibility measurements show that the three complexes display different antiferromagnetic coupling intensities.
Co-reporter:Haijuan Du, Chaohai Wang, Yao Li, Yunyin Niu and Hongwei Hou
RSC Advances 2015 vol. 5(Issue 90) pp:74065-74074
Publication Date(Web):26 Aug 2015
DOI:10.1039/C5RA13007G
The hydrothermal reaction of a mixture of (NH4)6Mo7O24·4H2O, a flexible tripodal ligand 1,3,5-tris-(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (TITMB) and metal salts at different temperatures resulted in four novel compounds, namely [H2TITMB]2[Mo12O38]·4H2O (1), [Zn(Mo2O7)(TITMB)] (2), [H3TITMB]2[Cd(β-Mo8O26)(H2O)2(α-Mo8O26)]·4H2O (3) and [H3TITMB]2[Co(β-Mo8O26)(H2O)2(α-Mo8O26)]·4.5H2O (4). The structures of compounds 1, 2, 3 and 4 were explored with IR spectroscopy, thermal gravimetric analysis (TGA), PXRD, UV-vis diffuse reflectance spectra and single-crystal X-ray diffraction in the solid state. In 1 the new type of isopolymolybdate unit [Mo12O38]4− shared ten distorted {MoO6} octahedra and two distorted {MoO5} tetragonal pyramid with four kinds of O atoms. And the unprecedented bimetallic oxide chain [Zn(Mo2O7)]n in compound 2 consisted of trigonal bipyramids and octahedra through sharing edges. Both compounds 3 and 4 are 3-D octamolybdate-based inorganic–organic hybrids consisting of the polyacid [α-Mo8O26]4− anions and novel infinite chains of [β-Mo8O26]4− anions covalently linked through [Cd(H2O)2]2+ groups or [Co(H2O)2]2+ groups. In addition, the electrochemical behavior and photocatalytic activities of the title compounds were also investigated.
Co-reporter:Chao-Hai Wang, Hai-Juan Du, Yao Li, Yun-Yin Niu and Hong-Wei Hou
New Journal of Chemistry 2015 vol. 39(Issue 9) pp:7372-7378
Publication Date(Web):16 Jul 2015
DOI:10.1039/C5NJ01240F
Two novel complexes based on multivalent organic cations and PbI2, {(tbp)2[Pb3I12]}n (1) (tbp = 1,3,5-tri(N-pyridinium methyl)benzene tribromide) and {(tbpm)[Pb3I9]·H2O}n (2) (tbpm = 1,3,5-tri(4-methylpyridiniummethyl) benzene tribromide), have been synthesized and characterized by X-ray diffractometry. Compound 1 has a trinuclear structure and compound 2 presents a new 1D iodoplumbate. Photochemical studies reveal the good photocatalytic performances of the two iodoplumbate hybrids. Furthermore, the side chain's effect on the fabrication of the iodoplumbate and the photocatalytic performances was also investigated.
Co-reporter:Huijun Li, Hongxin Cai, Zhouqing Xu, Yaxin Cai, Xin Li, Hongwei Hou
Inorganic Chemistry Communications 2015 Volume 55() pp:1-4
Publication Date(Web):May 2015
DOI:10.1016/j.inoche.2015.02.011
•A three-dimensional carboxylate-bridged MnII compound containing unique manganese chains has been synthesized.•Alternating Mn chain was arranged as unprecedented J1J2J3J1⋯ mode.•Magnetic susceptibility measurement reveals an antiferromagnetism behavior derived from the topology of the chain.A three-dimensional carboxylate-bridged MnII compound [Mn6(tci)4(H2O)3]·7H2O}n (1) (tci = tris(2-carboxyethyl) isocyanurate) have been synthesized. The structure contains unique manganese chains in which the MnII ions are alternatively bridged by carboxylate groups in different coordination modes. The first example of such alternating Mn chain shows Mn1–(COO)3–Mn2–(COO)2–Mn3–(COO)3–Mn1–(COO)3–Mn2-sequence arranged as J1J2J3J1S⋯ mode. Magnetic susceptibility measurement reveals an antiferromagnetism behavior derived from the topology of the chain. There is no suitable analytical expression for determining the exchange parameters in a 1-D Heisenberg ferrimagnet consisting of alternating interactions J1J2J3J1⋯. The best way to fit the magnetic behavior of these complexes is to proceed by using a Hamiltonian that corresponds to a 12-membered of S = 5/2 with 4 fragments repeating the sequence J1J2J3. The fit was performed by means of the computer program MAGPACK. The fitting for the observed magnetic data gives J1 = − 2.31 cm− 1, J2 = − 1.60 cm− 1, J3 = − 3.10 cm− 1, zJ′ = − 0.03 cm− 1 and g = 1.98, with R = 7.2 × 10− 3.A three-dimensional carboxylate-bridged MnII compound [Mn6(tci)4(H2O)3]·7H2O}n (1) containing unique manganese chains have been synthesized. The first example of such alternating Mn chain was arranged as J1J2J3J1⋯ mode. Magnetic susceptibility measurement reveals an antiferromagnetism behavior derived from the topology of the chain.
Co-reporter:Li-Na Zhang, Ai-Ling Liu, Ya-Xing Liu, Jia-Xiu Shen, Chen-Xia Du, Hong-Wei Hou
Inorganic Chemistry Communications 2015 Volume 56() pp:137-140
Publication Date(Web):June 2015
DOI:10.1016/j.inoche.2015.04.003
•A luminescent Eu-MOF with free phenanthroline N sites was synthesized.•Its high stability in water is very important for the practical application.•It exhibits highly sensitive and selective sensing of Cu2 + ion in aqueous solution.•The mechanism of the sensing properties was studied in detail.A luminescent europium metal–organic framework [Eu(HL)(L)(H2O)2]·2H2O (1) (H2L = (2,3-f)-pyrazino(1,10)phenanthroline-2,3-dicarboxylic acid) with uncoordinated phenanthroline nitrogen sites was hydrothermally synthesized. It exhibits highly sensitive and selective sensing of Cu2 + in aqueous solution. To the best of our knowledge, complex 1 is the first luminescent Eu-MOF with uncoordinated phenanthroline nitrogen sites for selective sensing of Cu2 + in aqueous solution. The probable sensing mechanism was discussed in detail.A luminescent Eu-MOF with uncoordinated phenanthroline nitrogen sites was hydrothermally synthesized. It exhibits highly sensitive and selective sensing of Cu2 + in aqueous solution.
Co-reporter:Hai-Juan Du, Chao-Hai Wang, Yao Li, Zhong-Cheng Yue, Lin-Rui Zhang, Li Li, Wen-Li Zhang, Yun-Yin Niu, Hong-Wei Hou
Inorganica Chimica Acta 2015 430() pp: 46-54
Publication Date(Web):
DOI:10.1016/j.ica.2015.02.024
Co-reporter:Zhouqing Xu, Wei Meng, Huijun Li, Hongwei Hou, and Yaoting Fan
Inorganic Chemistry 2014 Volume 53(Issue 7) pp:3260-3262
Publication Date(Web):March 24, 2014
DOI:10.1021/ic500004s
A FeII-based metal–organic framework (MOF), {[Fe2(pbt)2(H2O)2]·2H2O}n, undergoes an irreversible dehydration, which triggers changes in the catalytic and magnetic properties of the MOF. These property changes are attributed to the high-spin to low-spin transition of 7.1% center FeII, which is demonstrated by 57Fe Mössbauer, X-ray photoelectron spectroscopy, and UV/vis absorption spectra.
Co-reporter:Jianhua Qin, Yanyuan Jia, Huijun Li, Bei Zhao, Dongqing Wu, Shuangquan Zang, Hongwei Hou, and Yaoting Fan
Inorganic Chemistry 2014 Volume 53(Issue 2) pp:685-687
Publication Date(Web):January 7, 2014
DOI:10.1021/ic402598p
The conversion from a [2 + 2] nested double-helical column, {[Mn2(ptptp)(suc)(H2O)2]·1.5H2O}n (1), to a cationic spiral staircase, {[Mn2(ptptp)(suc)0.5(H2O)3]·Br·0.5H2O}n (2), has been achieved through ionic liquid anion stimulations under solvothermal conditions. The conversion does not change the antiferromagnetic interactions.
Co-reporter:Lu Liu, Jie Ding, Ming Li, Xiaofeng Lv, Jie Wu, Hongwei Hou and Yaoting Fan
Dalton Transactions 2014 vol. 43(Issue 33) pp:12790-12799
Publication Date(Web):17 Jun 2014
DOI:10.1039/C4DT01080A
A series of novel CdII coordination complexes, formulated as {[Cd(btbb)0.5(p-phda)]·H2O}n (1), [Cd(btbb)0.5(oba)]n (2), {[Cd2(btbb)(m-bdc)2(H2O)]·2H2O}n (3), {[Cd(btbb)0.5(btec)0.5(H2O)]·2H2O}n (4), [Cd(btbb)0.5(o-bdc)]n (5) and {[Cd2(btbb)(bptc)(H2O)]·4H2O}n (6) (btbb = 1,4-bis(2-(4-thiazolyl)benzimidazol-1-ylmethyl)benzene, H2phda = phenylenediacetic acid, H2oba = 4,4′-oxybis(benzoic acid), m-H2bdc = 1,3-benzenedicarboxylic acid, H4btec = 1,2,4,5-benzenetetracarboxylate, o-H2bdc = 1,2-benzenedicarboxylic acid, H4bptc = 3,3′,4,4′-benzophenone tetracarboxylic acid), have been obtained by solvothermal/hydrothermal reactions for the exploration of efficient photocatalytic degradation of organic dye pollutants. Complex 1 features a 6-connected 3D pcu α-Po primitive cubic topology net with the point symbol 412·63. Interestingly, complexes 2, 3 and 5 contain left- and right-handed helical chains (2: a 2-fold interpenetrating 3D architecture with {412·63}-pcu topology network; 3: a (3,6)-connected net with a vertex symbol (42·54·66·7·82)(4·62); 5: a (3,4)-connected 3,4L83 topology net with point symbol (42·6)(42·63·8)). Complex 4 exhibits a (3,4)-connected 3,4T48 topology net with point symbol (84·102)(8·102), while complex 6 possesses a (3,5)-connected 3,5L2 topology with the point symbol (42·6)(42·67·8). Furthermore, the photophysical studies indicate that the relatively narrow optical energy gaps of complexes 1–6 (<2.30 eV) calculated from the diffuse reflectivity spectra reflect their outstanding semiconductive nature. The photocatalytic properties of complexes 1–6 were studied in detail, and the results demonstrate their good photocatalytic activities in methylene blue (MB) degradation reactions, especially for complexes 3, 4 and 6 (3: 91.4%, 4: 92.7%, 6: 86.7%).
Co-reporter:Lu Liu, Xiaofeng Lv, Lin Zhang, Li'an Guo, Jie Wu, Hongwei Hou and Yaoting Fan
CrystEngComm 2014 vol. 16(Issue 37) pp:8736-8746
Publication Date(Web):18 Jul 2014
DOI:10.1039/C4CE01184H
Two new Mn(II) coordination polymers, namely {[Mn3L2(pbbm)]·CH3CN}n (1) and [Mn3L2(CH3CN)2]n (2) (pbbm = 1,1′-(1,5-pentane)bis-benzimidazole) have been prepared using a 3,4-bi(4-carboxyphenyl)benzoic acid (H3L) ligand under solvothermal conditions. Single-crystal X-ray diffraction studies indicate that 1 and 2 are both three-dimensional frameworks composed of trinuclear Mn(II) subunits. A topological analysis manifests that 1 is a 3-nodal (3,4,9)-connected new topology with a Schläfli symbol of (3·42)(3·42·63) (34·46·56·614·76); while 2 is a 4,8-c flu network topology with a Schläfli symbol of (46)(412·612·84). 1 and 2 possess excellent chemical resistance to boiling water and organic solvents. Variable temperature magnetization measurements (χMT–T and χM−1–T) make it clear that both complexes display ferrimagnetic interactions in the low-temperature region. The values from field-dependent magnetization measurements, M(H), do not reach clear saturation because of the magnetic anisotropy of the polycrystalline sample. Using alternating current (AC) susceptibility measurements, frequency-dependent peaks do not appear in all in-phase (χ′) and out-of-phase (χ′′) curves, indicating that there is no slow relaxation behavior of the magnetization. Markedly, the field-cooled (FC) and zero-field-cooled (ZFC) data of 1 display a divergence over the temperature range of 40–3.5 K, which could be on account of long-range magnetic ordering, or the impact of superparamagnetic behavior. Especially, 2 is based on a typical –J1J1J2– sequence, featuring a ferrimagnetic chain with a (5/2, 10/2) spin topology.
Co-reporter:Ming Li, Lu Liu, Lin Zhang, Xiaofeng Lv, Jie Ding, Hongwei Hou and Yaoting Fan
CrystEngComm 2014 vol. 16(Issue 28) pp:6408-6416
Publication Date(Web):04 Mar 2014
DOI:10.1039/C4CE00093E
Tuned by different aromatic polycarboxylates, six fascinating coordination polymers (CPs), namely, [Cd(pbmb)(p-bdc)]n (1), {[Zn3(pbmb)2(1,3,5-btc)2]·6H2O}n (2), {[Cd3(pbmb)3(1,3,5-btc)2(H2O)]·3H2O}n (3), {[Zn2(pbmb)(1,2,3-btc)(μ2-OH)]·H2O}n (4), [Cd(pbmb)(1,2,4,5-btec)0.5]n (5), and {[Cd(pbmb)(sdba)]·2H2O}n (6) (pbmb = 1,1′-(1,3-propane)bis-(2-methylbenzimidazole), p-H2bdc = 1,4-benzenedicarboxylic acid, 1,3,5-H3btc = 1,3,5-benzenetricarboxylic acid, 1,2,3-H3btc = 1,2,3 benzenetricarboxylic acid, 1,2,4,5-H4btec = 1,2,4,5-benzenetetracarboxylic acid, H2sdba = 4,4′-sulfonyldibenzoic acid), have been ideated and synthesized by hydrothermal reaction methods. Structural analyses reveal that complexes 1–3 feature three-dimensional (3D) structures (1: 4-connected 66 topology, 2: (3,4,6)-connected (65·7)(4·62)2(42·66·85·102) topology and 3: (2,3,4)-connected (65·8)2(63)2 topology), and the remaining CPs 4–6 exhibit 2D networks. The thermal stability and powder X-ray diffraction for 1–6 have been investigated as further properties. The optical band gaps are analyzed by diffuse-reflectance UV-vis spectra. Moreover, all of the materials manifest good photocatalytic activities for the degradation of methylene blue (MB) (1: 74%, 2: 41%, 3: 37%, 4: 76%, 5: 46%, 6: 75%, respectively) in water under the irradiation of a high-pressure mercury lamp.
Co-reporter:Huijun Li, Zhouqing Xu, Bei Zhao, Yanyuan Jia, Ran Ding, Hongwei Hou and Yaoting Fan
CrystEngComm 2014 vol. 16(Issue 12) pp:2470-2479
Publication Date(Web):06 Jan 2014
DOI:10.1039/C3CE41553H
A series of polymers containing MnII clusters varying from dinuclear, tetranuclear, hexanuclear, to rod-shaped uniform chains has been synthesized. The polymer [Mn4(Htci)2(ptptp)2(H2O)6]·8H2O (1) (H3tci = tris(2-carboxyethyl)isocyanurate, H2ptptp = 2-(5-{6-[5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl]pyridin-2-y-1H-1,2,4-triazol-3-yl}pyrazine) shows an interesting ladder based on dinuclear Mn clusters. The polymer {[Mn3(tci)2(pbbm)(H2O)3]·H2O}n (2) (pbbm = 1,1′-(1,5-pentanediyl)bis-1H-benzimidazole) has a 2D 3,6-connected framework with tetranuclear and dinuclear Mn clusters. The polymer {[Mn3(tci)2(bbbm)(H2O)3](H2O)}n (3) (bbbm = 1,1′-(1,4-butanediyl)bis-1H-benzimidazole) belongs an uncommon 3D 3,12-connected framework assembled by hexanuclear clusters. And the polymer {Mn(Htci)(dpp)}n (4) (dpp = 1,3-di(4-pyridyl)propane) based upon rod-shaped uniform Mn chains exhibits a 2D framework. Magnetic susceptibility measurements indicate that all of the polymers show weak antiferromagnetic interactions.
Co-reporter:Wei Meng, Zhouqing Xu, Jie Ding, Dongqing Wu, Xiao Han, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2014 Volume 14(Issue 2) pp:730-738
Publication Date(Web):January 7, 2014
DOI:10.1021/cg401601d
To search for effective photocatalysts in the field of cluster-based coordination complexes, we synthesized {[Cd2(dcpp)(beb)2 (H2O)]·H2O}n (1), [Cd2(dcpp)(bmb)(H2O)2]n (2), {[Cd2(dcpp)(2,2′-bipy)(H2O)2]·2H2O}n (3), and {[Cd2(dcpp)(4,4′-bipy)0.5(H2O)3]·H2O}n (4) by utilizing a butterfly-shaped multidentate carboxylic acid (4,5-di(4′-carboxylphenyl)phthalic acid) (H4dcpp)) and N-donor ligands (1,4-bis(2-ethylbenzimidazol-1-ylmethyl) benzene (beb), 1,4-bis(2-methylbenzimidazol-1-ylmethyl) benzene (bmb), 2,2′-bipyridine (2,2′-bipy), 4,4′-bipyridine (4,4′-bipy)). Complexes 1–4 are constructed based on different SBUs. Complexes 1 and 2 possess three-dimensional (3D) pillar-layered frameworks based on noncluster-type SBUs and dinuclear Cd2 clusters units, respectively. Complex 3 is a 3D porous structure building on Cd4 clusters SBUs. Complex 4 is constructed from rare infinite botryoid-like Cd cluster chains and exhibits a 3D complicated framework. The research on optical energy gaps of complexes 1–4 indicates that these complexes are potential semiconductive materials. Moreover, complexes 1–4 are applied to catalyze the reaction of photocatalytic degradation of methylene orange (MO) under high-pressure mercury lamp irradiation. Excitingly, they exhibit good photocatalytic properties in the presence of H2O2, and the degradation rates for 1–4 increase from 43% (without photocatalyst) to 97, 78, 85, and 67%, respectively, after 100 min of irradiation. The photoluminescent properties of complexes 1–4 were also studied.
Co-reporter:Lu Liu, Jie Ding, Chao Huang, Ming Li, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2014 Volume 14(Issue 6) pp:3035-3043
Publication Date(Web):April 23, 2014
DOI:10.1021/cg500295r
To systematically explore the effect of polynuclear complexes on photocatalytic degradation of the organic dyes, a series of coordination complexes containing CdII clusters, formulated as {[Cd3L2(H2O)5]·H2O}n (1), {[Cd3L2(hbmb)(H2O)2]·2.5H2O}n (2), {[Cd3L2(btbb)(H2O)2]·2EtOH·1.5H2O}n (3), and {[Cd6L4(bipy)2(H2O)6]·3H2O}n (4) (H3L = 3,4-bi(4-carboxyphenyl)-benzoic acid, hbmb = 1,1′-(1,6-hexane)bis(2-methylbenzimidazole), btbb = 1,4-bis(2-(4-thiazolyl)benzimidazole-1-ylmethyl)benzene, 4,4′-bipy = 4,4′-bipyridine), have been designed and synthesized. Complex 1 based on trinuclear CdII clusters exhibits a new (3,3,6)-connected 3D framework. 2 belongs to a (3,3,8,8)-connected tfz-d topology net with pillar-layered frameworks assembled by two kinds of trinuclear CdII clusters. 3 is a 3D pillar-layered framework, which features a (3,8)-connected tfz-d net based upon one kind of trinuclear CdII cluster. 4 presents a new 3D (3,6,10)-connected framework with dinuclear and tetranuclear clusters. The photocatalytic properties of complexes 1–4 have been studied in detail. Remarkably, 1–4 all reveal good photocatalytic activity in MB/MO degradation. The optical energy gap calculated by the diffuse reflectivity spectra of 1–4 are consistent with their degradation rates. Moreover, the experimental results further demonstrate that the cluster complexes containing different kinds of nuclei may exert different impact on the decomposition of disparate organic dyes.
Co-reporter:Chao Huang, Feixiang Ji, Lu Liu, Na Li, Haofei Li, Jie Wu, Hongwei Hou and Yaoting Fan
CrystEngComm 2014 vol. 16(Issue 13) pp:2615-2625
Publication Date(Web):23 Dec 2013
DOI:10.1039/C3CE42366B
Seven new coordination polymers (CPs), namely, {[Co3(sdba)3·2H2O·DMF]·2DMF}n (1), {[Co2(sdba)·(μ3-OH)·(trz)·H2O]·H2O}n (2), {[Co2(sdba)·(μ3-OH)·(atz)·H2O]·H2O}n (3), {[Co(sdba)·(ti)2·H2O]·1.5H2O}n (4), {[Cu(sdba)·H2O]·1.5H2O}n (5), {[Cu2(sdba)·(μ3-OH)·(trz)·H2O]·H2O}n (6) and {[Zn2(sdba)·(atz)2]·0.5H2O}n (7) (H2sdba = 4,4′-sulfonyldibenzoic acid, Htrz = 1H-1,2,4-triazole, Hatz = 1H-1,2,4-triazol-3-amine, Hti = 4-(1H-benzo[d]imidazol-2-yl)thiazole), have been solvothermally synthesized and characterized by IR spectroscopy, elemental analysis and X-ray single-crystal diffraction. Complex 1 displays a 6-connected three-dimensional (3D) framework with {412·63} pcu topology, which consists of two-dimensional (2D) zigzag sheets connected in an alternate fashion. Complexes 2, 3 and 6 are isostructural, exhibiting an 8-connected “onion” 3D framework with the first reported {36·410·56·66} whc1 topology. Complex 4 exhibits a one-dimensional (1D) helix chain, which is further connected by hydrogen bonds, giving a 2D supramolecular framework. Complex 5 reveals a 1D ∞-like chain. Compound 7 is a 3D metal–organic framework, which shows a tetranodal 3,3,4,4-c net with the point symbol {46·82·1012}{46·83·10}{46·8}{48·2} named whc2 topology. The solvent resistance properties of 1–7 have been investigated in detail. This demonstrates that with the introduction of rigid organic molecules (Htrz, Hatz, and Hti) as auxiliary ligands, complexes 2–4, 6 and 7 show remarkable hydrothermal stability and boiling organic solvent resistance. More importantly, an alternative strategy for the rational assembly of CPs with both good solvent resistance and intriguing structural topologies has been proposed. In addition, the luminescent properties of complexes 2, 6 and 7 are discussed, and the thermal stabilities of complexes 2 and 7 are also investigated.
Co-reporter:Liyan Fan, Linke Li, Bingjie Xu, Min Qiao, Jingjuan Li, Hongwei Hou
Inorganica Chimica Acta 2014 Volume 423(Part A) pp:46-51
Publication Date(Web):1 November 2014
DOI:10.1016/j.ica.2014.07.041
•Three coordination complexes based on mercapto-thiadiazole ligand were gained.•Complex 1 shows an in situ transformation of 4-Hptt into Hddc.•Complex 2 features a 2D grid layer.Three coordination complexes, namely, [Co(ddc)3] (1), [Zn(4-ptt)2·H2O]n (2) and [Pb(4-ptt)2]n (3), (Hddc = N,N-dimethyldithiocarbamic acid; 4-Hptt = 5-(4-pyridyl)-1,3,4-thiadiazole-2-thione) have been successfully synthesized under the same reaction conditions but tuned by different metal salts. Notably, in situ ligand reaction exists in the formation of complex 1, in which the ligand 4-Hptt reacted with DMF to generate the ligand Hddc. The X-ray single diffraction analysis reveals that 2 features a 2D layer structure, constructed from Zn(II) ions and 4-Hptt ligand. Complex 3 exhibits a 1D chain with 4-Hptt bridged four-coordinated Pb(II). Complexes 1–3 were characterized by elemental analyses, IR. The possible mechanism of the formation of Hddc for complex 1 has been discussed, and in addition, solid-state luminescent properties of polymers 2, 3 and ligand (4-Hptt) have also been investigated.One mononuclear complex [Co(ddc)3] (1), a 2D grid layer [Zn(4-ptt)2·H2O]n (2) and a 1D chain [Pb(4-ptt)2]n (3) were obtained. Notably, complex 1 shows an in situ transformation of 4-Hptt into Hddc. The possible mechanism of the formation of Hddc for complex 1 has been discussed, and solid-state luminescent properties of polymers 2, 3 and ligand (4-Hptt) have also been investigated.
Co-reporter:Chao Huang;Ran Ding; Chuanjun Song;Jingjing Lu;Lu Liu;Xiao Han; Jie Wu;Hongwei Hou; Yaoting Fan
Chemistry - A European Journal 2014 Volume 20( Issue 49) pp:16156-16163
Publication Date(Web):
DOI:10.1002/chem.201403162
Abstract
In our continuing quest to develop a metal–organic framework (MOF)-catalyzed tandem pyrrole acylation–Nazarov cyclization reaction with α,β-unsaturated carboxylic acids for the synthesis of cyclopentenone[b]pyrroles, which are key intermediates in the synthesis of natural product (±)-roseophilin, a series of template-induced Zn-based (1–3) metal-organic frameworks (MOFs) have been solvothermally synthesized and characterized. Structural conversions from non-porous MOF 1 to porous MOF 2, and back to non-porous MOF 3 arising from the different concentrations of template guest have been observed. The anion–π interactions between the template guests and ligands could affect the configuration of ligands and further tailor the frameworks of 1–3. Futhermore, MOFs 1–3 have shown to be effective heterogeneous catalysts for the tandem acylation–Nazarov cyclization reaction. In particular, the unique structural features of 2, including accessible catalytic sites and suitable channel size and shape, endow 2 with all of the desired features for the MOF-catalyzed tandem acylation–Nazarov cyclization reaction, including heterogeneous catalyst, high catalytic activity, robustness, and excellent selectivity. A plausible mechanism for the catalytic reaction has been proposed and the structure–reactivity relationship has been further clarified. Making use of 2 as a heterogeneous catalyst for the reaction could greatly increase the yield of total synthesis of (±)-roseophilin.
Co-reporter:Lin Zhang, Lu Liu, Ming Li, Chao Huang, Hong Xu, Hong-Wei Hou, Yao-Ting Fan
Polyhedron 2014 Volume 83() pp:197-204
Publication Date(Web):24 November 2014
DOI:10.1016/j.poly.2014.06.021
Three Cd(II) coordination polymers, namely, {[Cd2(bptp)2(H2O)4]·3H2O}n (1), {[Cd2(Hbptp)(BTC)(H2O)]·4H2O}n (2) and {[Cd2(H2bptp)(BTEC)]·H2O}n (3) (1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid and H4BTEC = 1,2,4,5-benzenetetracarboxylic acid), have been successfully isolated by employing the rigid N-heterocyclic ligand 2,6-bis(3-(pyrid-3-yl)-1,2,4-triazolyl)pyridine (H2bptp) and different aromatic polycarboxylates. Complex 1 performs a helical chain structure, which is extended into 3D supermolecular framework due to its strong hydrogen bonding interactions. 2 demonstrates a binodal 3,4-connected 2D grid with the point symbol of (42·62·8)(42·6), while complex 3 features an interesting 2D structure with its 1D double chain looking like a folded paper lantern. The optical band gaps were analyzed by diffuse-reflectance UV–Vis spectra. The photocatalytic experiments for these complexes reflect well on their activities for the decomposition of MB under the irradiation of high-pressure mercury lamp. Complexes 1 and 2 present extremely good photocatalytic properties with their photocatalytic activities increasing from 17% (without any catalyst) to 87% for 1 and 96% for 2 after 2 h of irradiation. In addition, the luminescent properties of 1–3 have also been investigated.Graphical abstractThree different CdII polymers based on ligand H2bptp and two different aromatic polycarboxylates have been successfully obtained under hydrothermal conditions. The optical band gaps analyzed by diffuse-reflectance UV–Vis spectra manifest that complexes 1–3 are potential semiconductive materials. Photocatalytic experiments for these complexes indicate that complex 1 and 2 present extremely good photocatalytic properties and can be rational candidates for the photocatalytic degradation of organic dyes pollutants.
Co-reporter:Bei Zhao, Hui-Jun Li, Yan-Yuan Jia, Qian-Qian Guo, Hong-Wei Hou, Yao-Ting Fan
Polyhedron 2014 Volume 68() pp:138-143
Publication Date(Web):28 January 2014
DOI:10.1016/j.poly.2013.10.022
Four new coordination polymers namely, [Zn(pddb)(H2O)]n (1), [Zn(pddb)]n (2), {[Cd2(pddb)2]·H2O}n (3) and [Cd(pddb)(H2O)2]n (4), have been solvothermally obtained. Among which, complexes 1 and 3 were prepared in presence of 4-nitrobenzoic acid, and complexes 2 and 4 not, respectively. Complex 1 shows a binodal 3,3-connected wavelike layer structure with the point symbol of (63)2. However, 2 performs a binodal 3,6-connected 3D coordination framework with the point symbol of (4·62)·(42·68·85). 3 exhibits a more complicated 3D periodic structure built on an infinite rod-shape secondary blocking units (SBUs), while 4 shows a double-chain structure, extended into 3D supramolecular framework through strong hydrogen bonding interactions. Furthermore, the study about photoluminescence properties of these four complexes and H2pddb ligand reveals that these diverse structures have significant influence on the photoluminescence signals.Four new coordination polymers namely, [Zn(pddb)(H2O)]n (1), [Zn(pddb)]n (2), {[Cd2(pddb)2]·H2O}n (3) and [Cd(pddb)(H2O)2]n (4), have been solvothermally obtained. Among which, complexes 1 and 3 were prepared in presence of 4-nitrobenzoic acid, and complexes 2 and 4 not, respectively. Furthermore, the study about photoluminescence properties of these four complexes and H2pddb ligand reveals that these diverse structures have significant influence on the photoluminescence signals.
Co-reporter:Ang-Ran Li, Qian-Qian Guo, Li Li, Hong-Wei Hou, Yao-Ting Fan
Polyhedron 2014 Volume 71() pp:17-23
Publication Date(Web):29 March 2014
DOI:10.1016/j.poly.2014.01.007
To systematically explore the influence of aromatic polycarboxylate ligands on building ZnII–BMP (1,5-bis(2-methylbenzimidazol) pentane) coordination polymers, four coordination polymers, namely {[Zn2(BMP)(PHSA)2]·H2O}n (1), [Zn4(BMP)2(BTEC)2(H2O)]n (2), [Zn2(BMP)(BTRC)(OH)]n (3), {[Zn3(BMP)(TCI)2(H2O)]·H2O}n (4) (H2PHSA = 2-phenylsuccinic acid, H4BTEC = benzene-1,2,4,5-tetracarboxylic acid, H3BTRC = benzene-1,3,5-tricarboxylic acid, H3TCI = Tris (2-carboxyethyl) isocyanurate) are synthesized by varying aromatic polycarboxylate ligands. Systematic structure analysis shows that 1–4 are comprised by one or more ZnII dimer in which carboxylate ligands bridge two metal ions forming dinuclear cores, and BMP links these cores. In 1, PHSA2− bridges ZnII ions to generate paddle-wheel dimer [Zn2(η1-COO)4] and these dimers are further linked by BMP to form 2D structure. 2 exhibits a layer with two different dimers: [Zn2(η1-BTEC4−)2] and [Zn2(η1-BTEC4−)(μ2-H2O)] indicating that bridge water have subtle influences on the coordination geometry. [Zn2(η1-BTRC3−)(μ2-OH)] dimers in 3 are further linked by two kind of wavelike layers constructing the 2-fold interpenetrated 3D architecture. 4 shows a 2-fold interpenetrated 3D architecture with dimeric centre. Notably, besides ZnII dimer [Zn2(η1-TCI3−)3], a monuclear ZnII ion exists as a terminal of ligand BMP enhancing photoluminescence intensity of 4 subtlely.To systematically explore the influence of aromatic polycarboxylate ligands on building ZnII–bmp (1,5-bis(2-methylbenzimidazol) pentane) coordination polymers, four coordination polymers with various dimeric centers have been hydrothermally synthesized.
Co-reporter:Li-Na Zhang, Xiao-Li Sun, Chen-Xia Du, Hong-Wei Hou
Polyhedron 2014 Volume 72() pp:90-95
Publication Date(Web):18 April 2014
DOI:10.1016/j.poly.2014.01.026
Five new metal–organic frameworks, namely [Cd(PA)(H2O)(DMF)2]n (1), {[Co(PA)(4,4′-bipy)(H2O) (CH3OH)]·DMF}n (2), {[Cd2(PA)2(4,4′-bipy)1.5(H2O)3]·2DMF·2H2O}n (3), {[Ni(PA)(bpp)(H2O)2]·DMF}n (4) and {[Cd(PA)(bpp)(CH3OH)]·CH3OH}n (5), (H2PA = pamoic acid, 4,4′-bipy = 4,4′-bipyridine, bpp = 1,3-bi(4-pyridyl) propane), have been solvothermally synthesized and characterized by elemental analysis, IR and X-ray diffraction. Complex 1 displays a zigzag chain structure, while both 2 and 4 are 2D layered polymers. In complex 3, two crystallographically independent Cd2+ ions are bridged by PA2− anions alternately to form an infinite (Cd–PA2−)n chain, which extends into a 2D network through 4,4′-bipy linkers. Complex 5 possesses a 3D framework with the point symbol of (83·102·12). Various weak interactions may play a key role in stabilizing the observed structures. Their luminescent properties and thermal stabilities have also been investigated. Complex 5 displays strong green luminescence with an emission maximum at 548 nm.Graphical abstractFive new metal–organic frameworks exhibiting structural diversity, from infinite chain to 3D framework, have been synthesized from reactions with pamoic acid (H2PA) under solvothermal conditions. The compound {[Cd(PA)(bpp)(CH3OH)]·CH3OH}n displays strong green luminescence with an emission maximum at 548 nm.
Co-reporter:Wei Meng;Huijun Li ;Zhouqing Xu ;Shanshan Du;Yunxia Li;Yanyan Zhu;Dr. Yi Han ; Hongwei Hou; Yaoting Fan; Mingsheng Tang
Chemistry - A European Journal 2014 Volume 20( Issue 10) pp:2945-2952
Publication Date(Web):
DOI:10.1002/chem.201303434
Abstract
Herein, a mechanism of stepwise metal-center exchange for a specific metal–organic framework, namely, [Zn4(dcpp)2(DMF)3(H2O)2]n (H4dcpp=4,5-bis(4′-carboxylphenyl)phthalic acid), is disclosed for the first time. The coordination stabilities between the central metal atoms and the ligands as well as the coordination geometry are considered to be dominant factors in this stepwise exchange mechanism. A new magnetic analytical method and a theoretical model confirmed that the exchange mechanism is reasonable. When the metathesis reaction occurs between CuII ions and framework ZnII ions, the magnetic exchange interaction of each pair of CuII centers gradually strengthens with increasing amount of framework CuII ions. By analyzing the changes of coupling constants in the Cu-exchanged products, it was deduced that Zn4 and Zn3 are initially replaced, and then Zn1 and Zn2 are replaced later. The theoretical calculation further verified that Zn4 is replaced first, Zn3 next, then Zn1 and Zn2 last, and the coordination stability dominates the Cu/Zn exchange process. For the Ni/Zn and Co/Zn exchange processes, besides the coordination stability, the preferred coordination geometry was also considered in the stepwise-exchange behavior. As NiII and CoII ions especially favor octahedral coordination geometry in oxygen-ligand fields, NiII ions and CoII ions could only selectively exchange with the octahedral ZnII ions, as was also confirmed by the experimental results. The stepwise metal-exchange process occurs in a single crystal-to-single crystal fashion.
Co-reporter:Lu Liu, Chao Huang, Zhengchuang Wang, Dongqing Wu, Hongwei Hou and Yaoting Fan
CrystEngComm 2013 vol. 15(Issue 35) pp:7095-7105
Publication Date(Web):11 Jul 2013
DOI:10.1039/C3CE40823J
Eight entangled coordination complexes, formulated as [M(hbmb)0.5(o-phda)]n [M = Zn (1), Cd (2)], {[M(hbmb)(p-phda)]·H2O}n [M = Zn (3), Cd (4)], [M(hbmb)0.5(oba)]n [M = Zn (5), Cd (6)], {[M(hbmb)(sdba)]m}n [M = Zn, m = 2 (7); m = 1, Cd (8)] (H2phda = phenylenediacetic acid, H2oba = 4,4′-oxybis(benzoic acid), H2sdba = 4,4′-sulfonyldibenzoic acid), have been prepared by hydrothermal reactions of the flexible ligand 1,1′-(1,6-hexane)bis-(2-methylbenzimidazole)) (hbmb) with metal ions in the presence of various dicarboxylate coligands. Isostructural complexes 1 and 2 reveal 6-connected self-penetrating three-dimensional (3D) frameworks with (44·610·8)-roa topologies. 3 and 4 display 4-fold interpenetrating 3D frameworks with 66-dia topologies. 5 and 6 exhibit 3D 2-fold interpenetrating 6-connected frameworks with (412·63)-pcu topologies. Both 7 and 8 are 3D frameworks constructed through unusual 2D → 3D parallel interpenetration of corrugated 2D (4,4) nets, of which 7 shows a 4-connected (44·62)2 topology and 8 presents a 4-connected 44·62 topology. A systematic structural comparison of four pairs of complexes shows that the frameworks can be tuned by various dicarboxylate coligands and changeable conformations of the hbmb ligand. In addition, the chemical stability, thermal stability and photoluminescent properties of complexes 1–8 have also been investigated.
Co-reporter:Huijun Li, Yi Han, Xiaofeng Lv, Shanshan Du, Hongwei Hou and Yaoting Fan
CrystEngComm 2013 vol. 15(Issue 18) pp:3672-3677
Publication Date(Web):05 Mar 2013
DOI:10.1039/C3CE00061C
Two isomorphous 3D noninterpenetrated CoII, NiII polymers with secondary building units (SBUs) of 1D ladder-shaped chains have been studied through their structures and magnetic properties. To systematically gain insight into the influence of metal ions on the magnetic behaviors, intermediate CoII-doped NiII polymers have been successfully synthesized. All of these complexes display noninterpenetrated 3D ladder structures and possess usual 3,6-connected ant nets. There are also large pores in the structures (49.1%). The magnetic results show that all of them display weak antiferromagnetic interactions. Such a strategy may have advantages for the generation of more interesting and adjustable magnetic materials.
Co-reporter:Yanyuan Jia;Huijun Li;Bei Zhao;Qianqian Guo;Hongwei Hou ;Yaoting Fan
European Journal of Inorganic Chemistry 2013 Volume 2013( Issue 3) pp:438-445
Publication Date(Web):
DOI:10.1002/ejic.201201092
Abstract
Three multinuclear PbII complexes―[Pb2(ptptp)2(H2O)2] (1), [Pb2(p-PDA)(Hptptp)2] (2), and [Pb4(o-PDA)2(ptptp)2]·2H2O (3) [H2ptptp = 2-(5-{6-[5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl]pyridin-2-yl}-1H-1,2,4-triazol-3-yl)pyrazine, H2PDA = phenylenediacetic acid]―have been synthesized under hydrothermal conditions. Complexes 1, 2, and 3 show di-, di-, and tetranuclear structures, respectively. The study of the chemical stability of the three complexes demonstrates their remarkable chemical resistance to boiling water and organic solvents. More importantly, complex 1 shows remarkable acid and alkali resistance, which is outstanding among metal–organic solids. The thermogravimetric analysis curve shows that complex 1 possesses high thermal stability (up to 491 °C). Furthermore, the fluorescence of complexes 1, 2, and 3 has also been investigated.
Co-reporter:Zhouqing Xu, Huijun Li, Angran Li, Wei Meng, Hongwei Hou, Yaoting Fan
Inorganic Chemistry Communications 2013 Volume 36() pp:126-129
Publication Date(Web):October 2013
DOI:10.1016/j.inoche.2013.08.003
•Three-dimensional complex, {[Co2(pbt)2(H2O)2] · 4.5H2O}n (1), has been synthesized.•Complex 1 exhibits a homochiral network containing octanuclear metallamacrocycles.•1 displays antiferromagnetic couplings through the 1,2,4-triazole-N1,N2 bridges.In this article, a chiral azolate-based octanuclear metallamacrocycle three-dimensional (3D) complexes {[Co2(pbt)2(H2O)2] · 4.5H2O}n (1) have been synthesized and characterized. Complex 1 crystallizes in the space group P43212 and displays a complicate homochiral three-dimensional (3D) framework containing octanuclear cobalt metallamacrocycles. The trizole-N1, N2 bridging cobalt trinuclear secondary building units (SBUs) in complex 1 provides a platform to investigate the magneto-structural correlations. The weak magnetic exchange of this complex is due to the asymmetric doubly 1,2,4-triazole-N1,N2 bridged SBUs which reduces the ineffective overlap between the orbits of paramagnetic central ions.Octanuclear metallamacrocycle-based three-dimensional (3D) complex {[Co2(pbt)2(H2O)2] · 4.5H2O}n (1) containing unidirectional helixes has been synthesized and characterised. Magnetic susceptibility measurements reveal that this complex display antiferromagnetic coupling.
Co-reporter:Chao Huang, Yao Wang, Changsen Wei, Na Li, Feixiang Ji, Jie Wu, Hongwei Hou
Inorganic Chemistry Communications 2013 Volume 32() pp:68-73
Publication Date(Web):June 2013
DOI:10.1016/j.inoche.2013.03.025
•SCSC transformations from [CoLCl2]2 (1) to [HgLCl2]2 (2) were attained.•SCSC transformations from 1 to a 2D complex [CdLSO4(H2O)2]n (3) were attained.•All the phenomena are observed via single crystal to single crystal transformations.•The exchange is a recurrent dissolving-exchange-crystallization process.Use of a rigidly conjugated clamp-like bis-pyridyl-bis-amide ligand N,N-bis-(3-pyridyl)isophthalamide (L), complex [CoLCl2]2 (1) with porous macrocycle structure was obtained under solvothermal conditions. When single crystals of 1 were immersed into the methanol solution of HgCl2 and CdSO4, new crystals of a bimetallic macrocyclic complex [HgLCl2]2 (2) and a two-dimensional (2D) corrugated sheet complex [CdLSO4(H2O)2]n (3) were attained, respectively. All these phenomena are observed through single crystal to single crystal (SCSC) transformations along with the metal–ligand bond breaking and the new metal–ligand bond formation. In addition, the determination of Scanning Electron Microscope (SEM) and Energy-Dispersive X-ray Spectrometry (EDS) reveals that the exchange is a recurrent dissolving-exchange-crystallization process of solvent-mediated mechanism.Complex [CoLCl2]2 (1) (L = N,N-bis-(3-pyridyl)isophthalamide) was obtained under solvothermal conditions. When crystals of 1 were immersed into the solution of HgCl2 and CdSO4, new crystals of [HgLCl2]2 (2) and [CdLSO4(H2O)2]n (3) were attained, respectively. All these phenomena are observed through SCSC along with the metal-ligand bond breaking and formation.
Co-reporter:Lu Liu, Yanhua Liu, Gang Han, Dongqing Wu, Hongwei Hou, Yaoting Fan
Inorganica Chimica Acta 2013 Volume 403() pp:25-34
Publication Date(Web):1 July 2013
DOI:10.1016/j.ica.2012.07.033
Five coordination complexes [Cd(hbmb)(tbi)]n (1), [Cd(hbmb)(adi)]n (2), [Zn(hbmb)0.5(atda)]n (3), {[Zn2(hbmb)(suc)1.5(OH)]·2H2O}n (4), and {[Zn2(hbmb) (fum)1.5(OH)]·2H2O}n (5) (H2tbi = 5-tert-butylisophthalic acid, H2adi = adipic acid, H2atda = 1,3-adamantanediacetic acid, H2suc = succinic acid, H2fum = fumaric acid, hbmb = 1,1′-(1,6-hexane)bis-(2-methylbenzimidazole)) have been hydrothermally synthesized and structurally characterized. Complex 1 is an undulated 2D structure with (63)2 topology, containing left- and right-handed helical chains. Complex 2 possesses a puckered two-dimensional (2D) network with 44·62 topologies symbol. Complex 3 exhibits a 2D (4, 4) parallelogram network and also owns left- and right-handed helical chains. Complexes 4 and 5 display 2D rectangular grids and can be simplified as a four-connected 44·62 topological network. Moreover, the photoluminescence properties and thermal stabilities of the five complexes were investigated.Graphical abstractFive new complexes have been obtained and characterized. Complex 1 exhibits an undulated 2D structure with (63)2 topology, containing left- and right-handed helical chains. Complex 2 presents puckered 2D networks with 44·62 topologies. Complex 3 possesses 2D (4, 4) parallelogram networks. Complexes 4 and 5 feature 2D rectangular grids with 44·62 topology.Highlights► 1,1′-(1,6-Hexane)bis-(2-methylbenzimidazole)(hbmb) is synthesized. ► Five complexes are obtained based on a flexible hbmb and different dicarboxylates. ► The complexes are structurally characterized through single crystal X-ray diffraction. ► The flexibility of hbmb and dicarboxylate coligands have an important effect on the features of resultant complexes.
Co-reporter:Dongqing Wu, Wei Meng, Lin Zhang, Lu Liu, Hongwei Hou, Yaoting Fan
Inorganica Chimica Acta 2013 Volume 405() pp:318-325
Publication Date(Web):24 August 2013
DOI:10.1016/j.ica.2013.06.014
•Four complexes with multiple helical characters are obtained upon a bis(triazole) ligand and dicarboxylate ligands.•The complexes are structurally characterized through single crystal X-ray diffraction.•Dicarboxylate coligands play a crucial role in tuning and enriching helical characters of coordination polymers.Based on the flexible bis(triazole) derivative 1,4-bis(1,2,4-triazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene (btmx) and dicarboxylate coligands, four new coordination polymers, namely, [Zn(phsa)(btmx)]n (1), [Zn(o-phda)(btmx)]n (2), {[Cd(p-phda)(btmx)(H2O)]·H2O}n (3), and [Cd(4,4′-sdba)(btmx)]n (4) have been synthesized under hydrothermal conditions. Structural analyses reveal that complexes 1–4 display diverse helical characters under the influence of dicarboxylates with different spacers. Complex 1 exhibits a 3D framework structure with left- and right-handed triple-stranded helices. Complex 2 features an irregular 2D grid constructed from double helices with (44·62) topology. The point symbol of complex 3 is (68·82)(63). Remarkably, it possesses a binodal (3,5)-connected 3D framework with the appearance of left- and right-handed triple-helical chains along the c axis. Moreover, left- and right-handed single-helical chains come into being through alternative arrangement of these triple-helical chains. To the best of our knowledge, coordination polymers containing triple- and single-helical chains along the same crystallographic axis are rare. The structure of complex 4 is a 2D grid comprising double helix components with (44·62) topology. These results indicate that the spacers of dicarboxylate coligands have significant effects on the helical character and ultimate frameworks. In addition, the investigation of photoluminescence properties reveals that complexes 1–4 show different photoluminescent behaviors.Graphical abstractFour new coordination polymers with diverse helical characters based on a flexible bis(triazole) ligand and different aromatic dicarboxylate coligands were synthesized, and their structures, topologies and photoluminescence were investigated. Moreover, the influence of dicarboxylate coligands on tuning helical characters were also discussed.
Co-reporter:Linke Li, Lulu Wei, Xiaoqin Si, Liyan Fan, Changhong Wang, Hongwei Hou
Inorganica Chimica Acta 2013 Volume 405() pp:279-287
Publication Date(Web):24 August 2013
DOI:10.1016/j.ica.2013.06.013
•Solvothermal reactions were used to prepare four intriguing network with versatile 3-pttH ligand.•Complexes 1 and 2 feature similar novel two-fold interpenetrating 3D framework with 66-dia topology.•The mercapto-thiadiazole ligand can build complicated and intriguing networks.•Complex 1 displays good solid-state fluorescence property.By combining one kind of N-/S-containing rigid ligand with metal ions Zn(II), Co(II), Ni(II) and Pb(II), we have solvothermally synthesized four mercapto-thiadiazole based coordination polymers: [Zn(3-ptt)2]n (1), [Co(3-ptt)2]n (2), [Ni(3-ptt)2]n (3) and [Pb(3-ptt)2] (4) (3-pttH = 2-(3-pyridine)-1H-1,3,4-thiadiazole-5-thioketone). As a result of various coordination modes of the versatile 3-ptt, four complexes exhibit structural diversity. 1 and 2 exhibit similar novel twofold interpenetrating 3D supramolecular framework with 66-dia topology embodying two types of left- and right-handed single-helical chains, 3 displays an attractive interconnected 1D chain structure and 4 presents a mononuclear structure. We also investigated their thermogravimetric (TG) and luminescent properties. Complexes 1 and 4 show different luminescence properties in solid state at room temperature and may be suitable as a candidate for potentially photoactive material.Constructed from mercapto-thiadiazole ligand, two twofold penetrated 3D complexes [Zn(3-ptt)2]n (1) and [Co(3-ptt)2]n (2), an interconnected 1D complex [Ni(3-ptt)2]n (3) and one mononuclear complex [Pb(3-ptt)2] (4) were obtained. The thermal stabilities of complexes 1–4 and luminescence properties of the complexes and ligand in the solid state have also been investigated in detail.
Co-reporter:Yi Han;Nicholas F. Chilton;Ming Li;Chao Huang; Hong Xu; Hongwei Hou;Boujemaa Moubaraki;Stuart K. Langley; Stuart R. Batten; Yaoting Fan; Keith S. Murray
Chemistry - A European Journal 2013 Volume 19( Issue 20) pp:6321-6328
Publication Date(Web):
DOI:10.1002/chem.201204115
Abstract
From a predesigned grid, [CuII5CuI4L6]⋅(I)2⋅13 H2O (1), in which LH2 was a pyrazinyl-triazolyl-2,6-substituted pyridine, we successfully synthesized an extended 3D complex, 1∞[{CuII5CuI8L6}{μ-[CuI3(CN)6]}2⋅2 CH3- CN] (2), that displayed unprecedented coexistence of all the five known coordination geometries of copper. Grid 1 displayed monovalent central metal exchange (CME) of CuI for AgI for the first time, as well as the formation of tri-iodide in the crystalline state. These systems were investigated for their magnetic properties. Remarkably, grid 1 showed much higher catalytic activity than the Ag-exchanged product for synthesis of a substituted triazole, 1-benzyl-4-phenyl-1H-1,2,3-triazole.
Co-reporter:Zhouqing Xu, Qiang Wang, Huijun Li, Wei Meng, Yi Han, Hongwei Hou and Yaoting Fan
Chemical Communications 2012 vol. 48(Issue 46) pp:5736-5738
Publication Date(Web):23 Apr 2012
DOI:10.1039/C2CC31590D
[8+12]-metallamacrocycle-based 3D frameworks {[Cu4(pbt)2(SO4)2(DMF)2(CH3OH)]·7H2O·DMF}n (1) and [12]-macrocycle 3D {[Cu2(pbt)(SO4)(DMSO)(CH3OH)2]·5H2O·CH3OH}n (2) have been obtained. Both complexes display antiferromagnetic couplings and high catalytic activity in the oxidative coupling reaction of 1-ethynylbenzene and oxazolidin-2-one.
Co-reporter:Huijun Li, Xia Wang, Yanyuan Jia, Bei Zhao, Ran Ding, Hongwei Hou and Yaoting Fan
CrystEngComm 2012 vol. 14(Issue 16) pp:5155-5157
Publication Date(Web):14 May 2012
DOI:10.1039/C2CE25393C
A novel Cu(II)-MOF {[Cu4(TTTMB)4(NO3)4(H2O)5]·(NO3)2·(I3)2·H2O}n containing polyiodide I3− was obtained through crystal to crystal transformation by immersing a CdII complex {[Cd3(TTTMB)4I2]·I4}n in an aqueous solution of Cu(NO3)2. There are two kinds of I3− arranged as infinite zigzag ⋯I3−⋯I3− chains between the layers of the Cu(II)-MOF.
Co-reporter:Li-Sha Song, Hong-Mei Wang, Yun-Yin Niu, Hong-Wei Hou and Yu Zhu
CrystEngComm 2012 vol. 14(Issue 15) pp:4927-4938
Publication Date(Web):11 Apr 2012
DOI:10.1039/C2CE25103E
Ten novel cation-induced complexes, {(BIQPT)2[Ag2I6]} (1), {[(BIQBT)CuI3]} (2), {(BIQHX)2[Cu4I8]·DMF} (3), {(BIQBT)1.5[MoOS3Cu3I4]·DMF} (4), {(BIQHX)[Ag4Br6]}n (5), {[(BIQHX)Ag4I6]}n (6), {(BIQHX)[Cu2(SCN)4]}n (7), {(BIQBT)[Cu2(SCN)4]}n (8), {(BIQPP)[Cu2(SCN)4]}n (9), {(BIQEH)[Cu2(SCN)4]}n (10) {BIQPT = 1,5-bis(isoquinoline)pentane, BIQBT = 1,4-bis(isoquinoline)butane, BIQHX = 1,6-bis(isoquinoline)hexane, BIQPP = 1,3-bis(isoquinoline)propane, BIQEH = 1,2-bis(isoquinoline)ethane} have been constructed via anion exchange reaction of bis(isoquinoline) ionic liquids. In these ten compounds, the anion structures ranged from mononuclear (2), dimer (1), tetranuclear oligomer (3 and 4), to 1D chain (5, 6,7 and 8) and 2D polymeric architectures (9 and 10). These results indicated that anion exchange reaction is an efficient approach for the preparation of cluster-functionalized ILs or IL-functionalized MOFs.
Co-reporter:Yong-Zhen Qiao, Wen-Zhen Fu, Jun-Ming Yue, Xiu-Cun Liu, Yun-Yin Niu and Hong-Wei Hou
CrystEngComm 2012 vol. 14(Issue 9) pp:3241-3249
Publication Date(Web):17 Feb 2012
DOI:10.1039/C2CE06687D
12 new cation-templated complexes, {(BMPB)[AgI3]} (BMPB = 1, 4-bis (methylpyridinium) benzene) (1), {(BPE)2[Ag2I6]} (BPE = 1, 2-bis (pyridinium) ethane) (2), {(BPB)[Ag2I4]} (BPB = 1, 4-bis (pyridinium) butane) (3), {(BPH)[Ag2I4]} (BPH = 1, 7-bis (pyridinium) heptane) (4), {(DIBP)[Ag2I4]} (DIBP = 1, 1′-diisopropyl-4, 4′-bipyridinium) (5), {(BPB)[Ag2Br4]} (6), {(BPP)[Ag2Br4]} (=1, 5-bis (pyridinium) pentane) (7), {(DEBP)[Ag2Br4]} (DEBP = 1, 1′-diethyl-4, 4′-bipyridinium) (8), {(BDMLB)[Ag2Br4]} (BDMLB = 1, 4-bis (dimethylimidazolium) butane) (9), {(BPIB·Br)[Ag(NCS)2]} (BPIB·Br = butane phenanthroline bromide) (10), {(DABP)[Ag4I6]} (DABP = 1, 1′-diamyl-4, 4′-bipyridinium) (11), {(BMLB)[Ag2Br2(NCS)2]} (BMLB = 1, 4-bis (methylimidazolium) butane) (12), have been synthesized via the self-assembly reaction in solution. Owing to the cooperative template effects from organic cations and halide/thiocyanate anion compounds 1–11 contain a mononuclear anion structure [AgI3]2− (1), a dimeric anion [Ag2I6]4− (2), linear chain [Ag2X4]2− (3–10) and a cubane-like based one-dimensional anionic chain [Ag4I6]2− (11) that are enclosed into the different cationic channels formed from the pyridinium, phenanthrolinium and imidazolium. While for 12, the compound possesses an infinite 2D supramolecular polypseudorotaxane penetrated by geminal dicationic groups.
Co-reporter:Hong-Mei Wang, Yi Han, Yun-Yin Niu, Zhen-Hua Zhang, Hong-Wei Hou and Yu Zhu
CrystEngComm 2012 vol. 14(Issue 9) pp:3125-3130
Publication Date(Web):24 Feb 2012
DOI:10.1039/C2CE06518E
Four novel heterothiometallic cluster polymers based on a [MoOS3Cu3] unit have been synthesized by the solution self-assembly of 4,4′-bipy (4,4′-bipy = bpy) with [NH4]2MoS2O2 and CuX (X = I, Br, or SCN) in the presence of different organic cation-templates [DMI]·I, [C6(Mim)2]·Br2, [C3(Mim)2]·Br2, and [BBP]·Br2: Compounds {[MoOS3Cu3I(μ-bpy)2.5]·2.5DMF}∞ (1), {[MoOS3Cu3I(μ-bpy)2.5] ·DMF}∞ (2), and {[MoOS3Cu3Br(μ-bpy)2.5]·2.5DMF}∞ (3) are isomorphous neutral 3D 4-fold interpenetrating architectures with a (6, 4) node, while polymer [MoOS3Cu3(NCS)(μ-bpy)2.5]∞ (4) is a 3D architecture with a (64 82) net displaying self-interpenetrating features. All of them have been characterized by single-crystal X-ray diffraction, elemental analysis, IR, TGA, and UV-vis. The results may provide fascinating insights into the template effect on the construction of the cluster-based coordination polymers.
Co-reporter:Yajuan Mu, Gang Han, Zhen Li, Xiaoting Liu, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2012 Volume 12(Issue 3) pp:1193-1200
Publication Date(Web):January 19, 2012
DOI:10.1021/cg201180u
To explore the influence of six structurally different polycarboxylate ligands H2L1 to H4L6 in the system Zn(II)/btmx, six coordination polymers, formulated as [Zn(btmx)(L1)]n (1), {[Zn(btmx)(L2)]·2H2O}n (2), {[Zn(btmx)(L3)]·1.5H2O}n (3), [Zn(btmx)(L4)]n (4), {[Zn4(btmx)3(L5)4(H2O)2]·4H2O}n (5), and [Zn(btmx)(H2L6)]n (6), have been obtained under similar conditions (btmx = 1,4-bis(1,2,4-triazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene, H2L1 = 1,3-benzenedicarboxylic acid, H2L2 = 1,4-benzenedicarboxylic acid, H2L3 = 1,3-adamantanedicarboxylic acid, H2L4= 1,3-adamantanediacetic acid, H2L5 = 4,4′-oxidibenzoic acid, and H4L6 = 3,3′,4,4′-benzophenone tetracarboxylic acid). The structure determination reveals that complexes 1 and 4 are two-dimensional (2D) layered networks and exhibit typical (4,4) topological nets. Complex 2 shows an undulating 2D (4,4)-network with 2-fold interpenetration. Complex 3 possesses a three-dimensional (3D) 3-fold interpenetrating 4-connected framework of 66-dia topology. Both 5 and 6 have different 3D interpenetrated motifs generated by 2D → 3D interpenetration. Complex 5 belongs to a 3D framework built from the interpenetration of 2D bilayers in an inclined mode, while 6 involves a parallel interpenetration between the adjacent 2D (4,4) layers. This work markedly indicates that the effect of polycarboxylate ligands is significant in the construction of these networks.
Co-reporter:Xianjuan Wang, Yanhua Liu, Chunying Xu, Qianqian Guo, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2012 Volume 12(Issue 5) pp:2435-2444
Publication Date(Web):March 23, 2012
DOI:10.1021/cg3000729
Five novel metal–organic frameworks with a 1,3,5-tris(triazol-1-ylmethyl)-2,4,6-trimethylbenzene (tttmb) flexible tripodal block, namely, {[Cd(tttmb)(atc)]·1.5H2O}n (1), {[Cd5(tttmb)2(tbi)5(H2O)4]·2H2O}n (2), {[Cd3(tttmb)2(bdc)3(H2O)3]·0.5H2O}n (3), {[Cd2(tttmb)2(btc)Cl]·3H2O}n (4), and {[Cd2(tttmb)2(btec)(H2O)3]·H2O}n (5) (H2atc = 1,3-adamantanedicarboxylic acid, H2tbi = 5-tert-butylisophthalic acid, H2bdc = 1,4-benzenedicarboxylic acid, H3btc = 1,2,4-benzenetricarboxylic acid, and H4btec = 1,2,4,5-benzenetetracarboxylic acid), have been synthesized. Complex 1 exhibits a two-dimensional structure with left- and right-handed helical chains arranged alternately. Complex 2 displays an intricate two-dimensional framework containing three layers with a 3,4,7-connected topology. It is notable that tbi2– takes on five different coordination modes in 2. Complex 3 presents a 3D 3,4-connected network with a point symbol of (63)2(64·82)2(63·83). The structure of complex 4 is a self-penetrating 3D 3,4,8-connected framework with left- and right-handed helical chains arranged alternately. Complex 5 shows a 3D pillar-layered framework, which can be simplified as a 3,4,5-connected 3D topology with a Schläfli symbol of (53)(52·62·7·9)(55·62·72·8). Moreover, the investigation of photoluminescence properties reveals that complexes 1–5 show different fluorescent behaviors.
Co-reporter:Yanyan Liu, Huijun Li, Yi Han, Xiaofeng Lv, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2012 Volume 12(Issue 7) pp:3505-3513
Publication Date(Web):May 24, 2012
DOI:10.1021/cg300237e
To investigate the influence of organic molecules with reactive functional groups as templates on the structures of the resulting MOFs, four novel complexes based on the pyridyl carboxylic acid ligand 5-(pyridin-4-yl)isophthalic acid (H2pyip), namely, [Mn3(pyip)2(HCOO)2(H2O)2]n (1), {[Co(pyip)(H2O)]·H2O}n (2), {[Mn2(pyip)2(H2O)4]·5H2O}n (3), and [Co(pyip)(EtOH)(H2O)]n (4), have been synthesized under solvothermal conditions. In the presence of 4,4′-bipyridyl as the template, 3D coordination framework 1 with the Schläfli symbol of (4·6·7) (42·5·65·73·82·9·11) was obtained. Using cyanoacetic acid as the template, we obtained 2D double-layered structure 2 with the Schläfli symbol of (43) (46·66·83). 3 and 4 are prepared in the absence of a templating agent. 3 features an infinite 2D network with a 1D water chain penetrating the 1D channel and further results in a 3D supramolecule through hydrogen-bond interactions. 4 contains two independent 2D networks that are further connected to a 2D double-layered supramolecular framework by hydrogen bonds. The template-assisted method is a potential approach for obtaining specific intriguing complexes that might be difficult to access by routine synthetic methods. Magnetic investigations revealed that both 1 and 2 exhibit weak antiferromagnetic interactions mediated by pyip2–.
Co-reporter:Huijun Li, Bei Zhao, Ran Ding, Yanyuan Jia, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2012 Volume 12(Issue 8) pp:4170-4179
Publication Date(Web):June 21, 2012
DOI:10.1021/cg3006794
The secondary building unit (SBU) has been identified as a useful tool in the synthesis of metal–organic frameworks (MOFs). Herein, we synthesized six novel Zn complexes, namely, {[Zn3(tci)2(DMF)2)]·2DMF·2CH3OH}n (1), {[Zn3(tci)2(DMSO)2(H2O)2]·2DMSO·3H2O}n (2), {[ZnNa(tci)(H2O)]·2H2O}n (3), {[Zn5(tci)2(OH)4(H2O)2]·2H2O}n (4), {[Zn3(tci)2(phen)2(H2O)2]·4H2O}n(5), and {[Zn3(tci)2(btb)2(H2O)2]·6H2O}n (6) by utilizing different SBUs (tci = tris(2-carboxyethyl) isocyanurate, phen = 1,10-phenanthroline, btb = 1,4-bis (1,2,4-triazole-1-ylmethyl) benzene). Complexes 1–4 were synthesized only by changing solvents, and complexes 5 and 6 were obtained by adding different auxiliary ligands on the same conditions. Structural analyses show that complexes 1 and 2 possess two-dimensional (2D) structures based on linear and triangular trinuclear Zn clusters. Complexes 3 and 4 exhibit 2D and three-dimensional (3D) frameworks built on rare infinite rod-shaped SBUs, while complex 5 belongs to a 3D framework with two kinds of left- and right-helical chains built from discrete dinuclear Zn clusters and mononuclear Zn atoms. Complex 6 exhibits high-connected 3D framework based on extended linear trinuclear Zn clusters.
Co-reporter:Qianqian Guo, Chunying Xu, Bei Zhao, Yanyuan Jia, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2012 Volume 12(Issue 11) pp:5439-5446
Publication Date(Web):September 27, 2012
DOI:10.1021/cg3010272
Five interesting interpenetrating networks, namely, [Co(p-bdc)(beb)0.5]n (1), {[Co(p-bdc)(bmb)]·H2O}n (2), {[Co(p-bdc)(bmp)]·H2O}n (3), {[Zn(p-bdc)(bmp)]·H2O}n (4), and [Zn2(p-bdc)2(bmp)(H2O)2]n (5) [p-H2bdc = 1,4-benzenedicarboxylic acid, beb = 1,4-bis(2-ethylbenzimidazol-1-ylmethyl)benzene, bmb = 1,4-bis(2-methylbenzimidazol-1-ylmethyl)benzene, and bmp = 1,5-bis(2-methylbenzimidazol) pentane], have been synthesized by employing mixed ligands of various benzimidazole-based ligands with p-H2bdc. Complex 1 possesses a 2-fold interpenetrating 3D framework with (412·63)-pcu topology. Complex 2 exhibits a 3-fold interpenetrating 3D network with 66-dia topology, and complex 3 displays a 4-fold interpenetrating 3D diamond network containing Co/bmp left- and right-handed helical chains. Obviously, with the reducing of the steric hindrance of the N-donor ligand, complexes 1–3 show interpenetrating networks from 2-fold to 3-fold and 4-fold. Complex 4 is isostructural to 3 and also forms a 4-connected 3D framework with a diamond topology. Complex 5 features a 3D framework generated by 2D → 3D interpenetration and exhibits (82·10)2 topology. Our study shows that the steric hindrance changing of ligands can tune the final interpenetrating networks directly.
Co-reporter:Yanyuan Jia;Huijun Li;Qianqian Guo;Bei Zhao;Ying Zhao;Hongwei Hou ;Yaoting Fan
European Journal of Inorganic Chemistry 2012 Volume 2012( Issue 18) pp:3047-3053
Publication Date(Web):
DOI:10.1002/ejic.201200013
Abstract
Two template-induced supramolecular isomers [Pb(2,3-pyde)]n (1 and 2; 2,3-pyde = pyridine-2,3-dicarboxylate) have been synthesized under hydrothermal conditions. Complex 1 displays a 2D network with a point symbol of (42·64)2, whereas complex 2 exhibits a 3D framework with a point symbol of (46·64)2. The study of the stability of the isomers demonstrates that they have high thermal stability and excellent chemical resistance to boiling water and common organic solvents. Interestingly, the two polymers evidently possess different fluorescent properties although they have the same chemical component.
Co-reporter:Jie Wu, Chao Huang, Leixia Fu, Pei Wang, Chuanjun Song, Changjian Song, Haiyu Wang, Hongwei Hou, Junbiao Chang
Inorganic Chemistry Communications 2012 Volume 19() pp:23-26
Publication Date(Web):May 2012
DOI:10.1016/j.inoche.2012.01.021
Solvothermal synthesis of an achiral ligand N,N-bis(3-pyridyl) isophthalamide (bpip) with ZnSO4 under 120 °C yield a novel compound, [Zn(bpip)SO4]n, which displays chiral self-assembly into an infinite double-stranded helical coordination polymer consisting of two single-stranded helices with the same P handedness. These chiral infinite double-stranded helical chains are further interwoven by the 1D Zn–SO4–Zn chains to form a novel 3D framework structure with a rare 65.10 topology. On the basis of the results of TG-DSC analyses, the structure is thermally stable up to ~ 467.4 °C.A highly stable 3D chiral coordination polymer consisting of two single-stranded helices with the same P handedness based on achiral ligand bpip is reported here. These chiral infinite double-stranded helical chains are interwoven with 1D S–O–Zn–O–S chains forming a 3D framework structure with novel 65.10 topology.Highlights► A 3D homochiral polymer based on an achiral ligand has been synthesized. ► Complex 1 exhibits interwoven of double-stranded helices and 1D metal-SO4-metal chains. ► The structure of 1 exhibits a rare 65.10 topology. ► The structure of 1 is thermally stable up to ~ 467.4 °C.
Co-reporter:Yanhua Liu, Lu Liu, Xianjuan Wang, Long Cheng, Hongwei Hou, Yaoting Fan
Inorganic Chemistry Communications 2012 Volume 21() pp:114-117
Publication Date(Web):July 2012
DOI:10.1016/j.inoche.2012.04.026
The reaction of the flexible tripodal ligand 1,3,5-tri(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene (tttmb) and Zn(II) with 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (3,3′,4,4′-bptda) gives a novel 3D coordination polymer {[Zn1.5(tttmb)(Hbptc)]·H2O}n (1) (H4bptc = 3,3′,4,4′-benzophenone tetracarboxylic acid). In 1, the ancillary Hbptc3– groups connect Zn(II) ions to form a 2D layered structure. The tttmb ligands further link the 2D structure to generate a fascinating tridimensional polymeric architecture containing infinite 1D single-stranded helical chains of the same M handedness.{[Zn1.5(tttmb)(Hbptc)]·H2O}n (1) has been synthesized via the reaction of a flexible ligand tttmb and Zn(II) in the presence of ancillary 3,3',4,4'-bptda group. In 1, Hbptc3– connect Zn(II) ions to form a 2D layer, further linked by tttmb to generate a 3D complex containing 1D left-stranded helical chains.Highlights► A fascinating 3D homochiral helical compound has been prepared. ► The achiral ligand has the potential to form homochiral compounds. ► The ancillary 3,3′,4,4′-bptda can effectively tune the final structural feature.
Co-reporter:Jie Wu, Pei Wang, Chao Huang, Leixia Fu, Changjian Song, Hongwei Hou, Junbiao Chang
Inorganic Chemistry Communications 2012 Volume 15() pp:301-304
Publication Date(Web):January 2012
DOI:10.1016/j.inoche.2011.11.008
Use of a C3-symmetric facial ligand N,N’,N”-tris(3-pyridyl)-1,3,5-benzenetricarboxamide (L1), three porous MOFs, [CdCl2(aas-L1)]n (1), [HgI2(sss-L1)]n (2) and [CoCl2(ass-L1)(EtOH)]2 (3), were obtained under solvothermal conditions. Complex 1 exhibits a fascinating 2D two interwoven nets consisting of sandwich-like channels. Compound 2 shows an infinite 1D polymeric chain in herringbone fashion running along a-axis. The hydrogen-bonding interactions further link the molecules into 2D extended structure with 48-membered macrocycles. In the binuclear complex 3, two metal centers are bridged by two ligands, producing a 28-membered ring. The macrocyclic subunits further self-assemble into an open-framework structure with porous system via the hydrogen-bonding interactions. Furthermore, the luminescence properties of these compounds have been studied.Three porous MOFs have been hydrothermally synthesized via the reaction of a C3-symmetric facial ligand L1 and MX2 (M = Cd, Hg and Co) under different temperature. Sing crystal X-ray diffraction revealed that complex 1 exhibits a fascinating 2D two interwoven nets consisting of sandwich-like channels. Compounds 2 shows an infinite 2D extended structure with 48-membered macrocycles via the hydrogen-bonding interactions. However, Complex 3 exhibits an open-framework structure with 28-membered macrocycles. The luminescence properties of them were also investigated at room temperature in the solid state.Highlights► Three MOFs based on a C3-symmetric triangular facial ligand have been synthesized. ► Complex 1 exhibits 2D two interwoven nets with unique (3,4,6)-connected topology. ► Hydrogen bonding interactions are driving force for the construction of MOFs. ► Coordiantion polymers 1 and 2 possess strong luminescence.
Co-reporter:Jinpeng Li, Xiaofang Li, Huijuan Lü, Yanyan Zhu, Huan Sun, Yuexin Guo, Zhifang Yue, Jin’an Zhao, Mingsheng Tang, Hongwei Hou, Yaoting Fan, Junbiao Chang
Inorganica Chimica Acta 2012 Volume 384() pp:163-169
Publication Date(Web):1 April 2012
DOI:10.1016/j.ica.2011.11.058
Four Hg(II)-containing complexes based on methylenebis(1,1′-benzimidazole) (mbbz), namely, [HgCl2(mbbz)]n (1), [HgBr2(mbbz)]n (2), [HgI2(mbbz)]n (3) and [HgI2(mbbz)]3 (4) have been synthesized and structurally characterized. Single-crystal X-ray diffraction reveals that complexes 1, 2 and 3 are isostructural exhibiting the 1-D double helical chain structures. After changing the solvent media, we obtained a trinuclear cage-like structure 4, which is isomeric with 3. Both experimental results and the theoretical calculation proved that the solvent is crucial to the structure of complexes. The fluorescence properties of the four complexes are also investigated and it is apparent that fluorescence intensity decreases as the atomic weight increases in the order of Cl−, Br− and I−. The subtle structure and fluorescence signal changes of these complexes indicate that both the solvents and halide anions have remarkable impact on the resultant complexes.Graphical abstractFour Hg(II)-containing complexes have been synthesized and characterized. Complexes 1, 2 and 3 exhibit the same 1-D double helical structures. After changing the solvent, a trinuclear cage-like 4 which is isomeric with 3 is obtained. The solvent effects were studies by theoretical calculation. Their fluorescence properties are also investigated.Highlights► Four Hg(II)-containing complexes have been synthesized and characterized. ► Complex 4 is isomeric with 3 and they are obtained from different solvent. ► Calculated results prove that solvent effects have influence on their structures. ► Halide anions of complexes have different impacts on their fluorescence properties.
Co-reporter:Lu Liu, Xiaoli Li, Chunying Xu, Gang Han, Ying Zhao, Hongwei Hou, Yaoting Fan
Inorganica Chimica Acta 2012 Volume 391() pp:66-74
Publication Date(Web):30 August 2012
DOI:10.1016/j.ica.2012.04.043
To explore the influence of isomeric benzenedicarboxylates on the self-assembly of coordination frameworks, six mixed-ligands Zn(II)/Co(II) coordination complexes, [Zn(pbmb)(1,4-bdc)]n (1), {[Co(pbmb)(1,4-bdc)]·1.5H2O}n (2), [M(pbmb)(1,3-bdc)]n [M = Zn (3) or Co (4)], and [M(pbmb)(1,2-bdc)]n [M = Zn (5) or Co (6)] (pbmb = 1,1′-(1,3-propane)bis-(2-methylbenzimidazole), 1,2-bdc = 1,2-benzenedicarboxylic acid, 1,3-bdc = 1,3-benzenedicarboxylic acid, and 1,4-bdc = 1,4-benzenedicarboxylic acid), have been obtained and structurally characterized. Structural analyses reveal that complexes 1 and 2 display 2D (4, 4) networks, of which complex 1 contains left- and right-handed helical chains arranged alternately and 2 owns a well-known paddle-wheel binuclear clusters. Complexes 3 and 4 feature 2D networks with 63 topologies, and complexes 5 and 6 exhibit 1D double-chain structures. Additionally, complexes 1–6 present high thermal stabilities, as well as 1, 3, and 5 show different photoluminescence behaviors in the solid state.Graphical abstractSix new complexes have been obtained and characterized. Complexes 1 and 2 display 2D (4, 4) networks, of which 1 contains left- and right-handed helical chains arranged alternately and 2 owns a well-known paddle-wheel binuclear clusters. Complexes 3 and 4 feature 2D networks with 63 topologies, and complexes 5 and 6 exhibit 1D double-chain structures.Highlights► 1,1’-(1,3-propane)bis-(2-methylbenzimidazole) (pbmb) is synthesized. ► Six complexes are obtained based on a flexible pbmb and isomeric benzenedicarboxylates. ► The complexes are structurally characterized through single crystal X-ray diffraction. ► Isomeric benzenedicarboxylates play a crucial role in the construction of coordination complexes.
Co-reporter:Huijuan Lü, Yajuan Mu, Jinpeng Li, Dongqing Wu, Hongwei Hou, Yaoting Fan
Inorganica Chimica Acta 2012 Volume 387() pp:450-454
Publication Date(Web):30 May 2012
DOI:10.1016/j.ica.2012.01.022
Reaction of methylene-bis(1,1′-benzimidazole) (mbbz) with CdI2 produces a complex [Cd(mbbz)I2]3 (1) containing the soft coordinated I− anions, which shows a trinuclear cage-like structure. Immersing complex 1 into the aqueous solution of NaN3, we obtained the exchanged product [Cd(mbbz)2(N3)2]n (2). The single-crystal X-ray diffraction shows that complex 2 presents a 3D 2-fold interpenetrating 4-connected framework with 66-dia topology. The results indicate that the soft coordinated I− anions can be completely exchanged by borderline N3− anions, simultaneously, accompanying the structural transformation from a trinuclear cage to a 3D framework. Furthermore, the AFM and EDS data reveal that the exchange is a recrystallization process with solvent-mediated mechanism.Graphical abstractThe soft coordinated I− anions in [Cd(mbbz)I2]3 (1) were exchanged by borderline N3− anions to give the exchanged product [Cd(mbbz)2(N3)2]n (2). The single crystal structural analysis of the two complexes shows the structural transformation from a trinuclear cage to a 3D 2-fold interpenetrated framework has occurred. Based on AFM and EDS data we confirm that strong coordination anions can be replaced by weak ones, and the exchange is a recrystallization process with solvent mediated mechanism.Highlights► The precursor [Cd(mbbz)I2]3 containing soft coordinated I− anions was synthesized. ► The precursor can transform into product [Cd(mbbz)2(N3)2]n via anion exchange. ► The structural transformation is from a trinuclear cage to a 3D framework. ► The soft coordinated I− anions can be exchanged by N3− anions. ► The exchange is a recrystallization process with solvent mediated mechanism.
Co-reporter:Jingjing Zhao, Linke Li, Changhong Wang, Wenju Li, Ruina Wang, Xiaofang Zheng, Hongwei Hou
Inorganic Chemistry Communications 2012 20() pp: 205-208
Publication Date(Web):
DOI:10.1016/j.inoche.2012.03.009
Co-reporter:Yi Han; Hong Xu;Yanyan Liu;Huijun Li; Hongwei Hou; Yaoting Fan; Stuart R. Batten
Chemistry - A European Journal 2012 Volume 18( Issue 44) pp:13954-13958
Publication Date(Web):
DOI:10.1002/chem.201201559
Co-reporter:Jin Jin, Weiyin Wang, Yanhua Liu, Hongwei Hou and Yaoting Fan
Chemical Communications 2011 vol. 47(Issue 26) pp:7461-7463
Publication Date(Web):31 May 2011
DOI:10.1039/C1CC12142A
The first hexagonal octadecanuclear Ag macrocycle [Ag18(TTTMB)12](NO3)18·30H2O has been hydrothermally synthesized. The outside and inner diameters of the unprecedented architecture are about 27.72(13) Å and 15.37(7) Å, respectively. This complex displays a huge increase in the intensity and lifetime of phosphorescence with decreasing temperature.
Co-reporter:Junhong Fu, Huijun Li, Yajuan Mu, Hongwei Hou and Yaoting Fan
Chemical Communications 2011 vol. 47(Issue 18) pp:5271-5273
Publication Date(Web):31 Mar 2011
DOI:10.1039/C1CC10251F
{[Cu6(TTTMB)8(OH)4(H2O)6]·8(NO3)·34.5H2O}n can reversibly transform to {[Cu6(TTTMB)8I3]·9I·26H2O}n upon a single crystal to single crystal process. The transformation is accompanied by the formation of weak Cu2+⋯I− interactions and changes in the coordination numbers, as well as modulation in their properties.
Co-reporter:Huijun Li, Hongchang Yao, Erpeng Zhang, Yanyuan Jia, Hongwei Hou and Yaoting Fan
Dalton Transactions 2011 vol. 40(Issue 37) pp:9388-9393
Publication Date(Web):15 Aug 2011
DOI:10.1039/C1DT10822K
The crystal structures and magnetic properties of two novel polyclusters {[Cu3(tci)2(H2O)2]·12H2O}n (1) and {[Cu3(tci)2(H2O)2]·6H2O}n (2) (tci = tris(2-carboxyethyl) isocyanurate) are investigated. The X-ray crystallographic analysis reveals that they contain interesting infinite alternating chains of dinuclear paddle-wheel copper and mononuclear copper units arranged in ABBA magnetism exchange mode. Variable-temperature magnetic susceptibility measurements on the two polyclusters show strong antiferromagnetism couplings between copper ions with exchange interactions J = −181.4 cm−1, zj′ = −0.31 cm−1 for 1, J = −170 cm−1, zj′ = −0.42 cm−1 for 2. With the aim of studying magneto-structural correlation, we synthesized a three-dimensional polymer [Cu3(tci)2(py)4(H2O)2]n (3) based on isolated dinuclear cluster and mononuclear copper units. Fitting the susceptibility data yielded J = −176.1 cm−1, zj′ = −0.084 cm−1 for 3.
Co-reporter:Lu-Fang Ma, Xiu-Qin Li, Li-Ya Wang and Hong-Wei Hou
CrystEngComm 2011 vol. 13(Issue 14) pp:4625-4634
Publication Date(Web):
DOI:10.1039/C1CE05308F
Co-reporter:Yajuan Mu, Gang Han, Shuying Ji, Hongwei Hou and Yaoting Fan
CrystEngComm 2011 vol. 13(Issue 19) pp:5943-5950
Publication Date(Web):10 Aug 2011
DOI:10.1039/C1CE05129F
Four new coordination polymers, namely, {[Cd(btmx)(BTEC)0.5(H2O)]·H2O}n (1), {[Cd(btmx)1.5(1,2,4-HBTC)]·(H2O)2}n (2), {[Co(btmx)(HBTC)]·2H2O}n (3) and [Co(btmx)(1,4-BDC)]n (4) (btmx = 1,4-bis(1,2,4-triazol-1-ylmethyl)-2,3,5,6-tetramethylbenzene, H4BTEC = 1,2,4,5-benzenetetracarboxylic acid, 1,2,4-H3BTC = 1,2,4-benzenetricarboxylic acid, 1,3,5-H3BTC = 1,3,5-benzenetricarboxylic acid and 1,4-H2BDC = 1,4-benzenedicarboxylic acid) have been obtained under hydrothermal conditions and characterized structurally. Complex 1 is a 3D 3-fold interpenetrating (4,4)-connected net with (4·64·8)(42·62·82) topology. Complex 2 displays a 2D cabinet-like structure with infinite 1D double Cd–btmx chains. Complex 3 possesses a 3D 3-fold interpenetrating 4-connected framework with 66-dia topology. Complex 4 exhibits a (4,6)-connected 3D pillar-layered structure with point symbol of (44·62)(44·610·8). The structural differences of these complexes demonstrate that the flexible ligand btmx and aromatic polycarboxylate anions play critical roles in the formation of the resulting frameworks. Furthermore, the photoluminescent properties of 1 and 2 have been studied in the solid state at room temperature.
Co-reporter:Chunying Xu, Qianqian Guo, Xianjuan Wang, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2011 Volume 11(Issue 5) pp:1869-1879
Publication Date(Web):March 25, 2011
DOI:10.1021/cg200052t
To systematically explore the influence of the spacer angles and lengths of dicarboxylate coligands on building ZnII-bmb [1,4-bis(2-methylbenzimidazol-1-ylmethyl)benzene] meso-helical coordination polymers, we synthesized seven metal−organic frameworks {[Zn(bmb)0.5(o-bdc)(H2O)]·0.5(bmb)·H2O}n (1), {[Zn(bmb)(2,6-pydc)]·2H2O}n (2), [Zn(bmb)(m-bdc)]n (3), [Zn(bmb)0.5(p-bdc)·H2O]n (4), [Zn(bmb)(fum)]n (5), {[Zn(bmb)(suc)]·1.5H2O}n (6), and {[Zn(bmb)(glu)]·H2O}n (7) (o-H2bdc = 1,2-benzenedicarboxylic acid, 2,6-H2pydc = 2,6-pyridinedicarboxylic acid, m-H2bdc = 1,3-benzenedicarboxylic acid, p-H2bdc = 1,4-benzenedicarboxylic acid, H2fum = fumaric acid, H2suc = succinic acid, and H2glu = glutaric acid) through rationally varying the organic acid linkers. Structural analyses reveal that complexes 1−7 display diverse helical characters under the influence of dicarboxylates with different spacers. In complexes 1, 2, 3, and 7, the bmb ligands adopt trans-conformation bridging ZnII ions to form rare meso-helices, which are further extended and decorated by different dicarboxylate coligands. Complex 4 exhibits a fascinating Borromean topology with three parallelly interlocked 63-hcb networks, in which p-bdc2- and bmb with trans-conformation are linked by ZnII ions to form a charming meso-helical chain. Complex 5 displays a 3-fold interpenetrated 3D diamonded network containing ZnII/bmb/fum left- and right-handed helical microchannels. Complex 6 features unusual interweaved meso-helices constructed by cis- and trans-conformational bmb, which is the second example of tetra-flexural helix with four spiral shafts in one helical chain. In addition, the suc2- anions further link ZnII-bmb meso-helices to form a 3D framework. These results indicate that the spacers of dicarboxylate coligands and the conformations of bmb have important effects on the meso-helical characters and ultimate frameworks. Moreover, the investigation of photoluminescence properties of 1−7 reveals that the helical feature plays an important role in reducing photoluminescent intensities.
Co-reporter:Yajuan Mu, Junhong Fu, Yajing Song, Zhen Li, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2011 Volume 11(Issue 6) pp:2183
Publication Date(Web):April 20, 2011
DOI:10.1021/cg101494t
Six new metal–organic frameworks, namely, {[Co(btmb)(HBTC)]·2H2O}n (1), {[Co3(btmb)3(BTC)2(H2O)2]·6H2O}n (2), {[Co3(btmb)3(BTC)2(H2O)4]·2H2O}n (3), {[Ni3(btmb)3(BTC)2(H2O)4]·2H2O}n (4), [Cu(btmb)(HBTC)]n (5), and [Cu(btmb)(NDC)]n (6) (H3BTC = 1,3,5-benzenetricarboxylic acid, H2NDC = 1,2-benzenedicarboxylic acid, and btmb = 4,4′-bis(1,2,4-triazol-1-ylmethyl)biphenyl), have been synthesized under hydrothermal conditions. The structure of 1 is a 6-connected self-penetrating three-dimensional (3D) framework with 44·610·8 topology. Complex 2 exhibits a trinodal (3,4)-connected topology with a Schläfli symbol of (62·84)(64·82)(63). Both complexes 3 and 4 possess 3D pillar-layered structures with a Schläfli symbol of (62·8·103)(64·8·10)(6·102). Complex 5 is also a 3D polymer with a pillar-layered framework, which can be simplified as the (63)(69·8) topology. Complex 6 shows a 4-connected 3D framework with a Schläfli notation of (65·8)2. Furthermore, complexes 1–6 as heterogeneous catalysts were studied in the green catalysis process of the oxidative coupling of 2,6-dimethylphenol (DMP) to poly(1,4-phenylene ether) (PPE) and diphenoquinone (DPQ). The results show that these complexes exhibit different catalytic activities; both the Cu complexes are catalytically active by showing high conversion of DMP and high selectivity of PPE, and they exhibit great potential as recyclable catalysts.
Co-reporter:Yi Han, Zhenhua Zhang, Yanyan Liu, Yunyin Niu, Degang Ding, Benlai Wu, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2011 Volume 11(Issue 8) pp:3448
Publication Date(Web):June 8, 2011
DOI:10.1021/cg200250m
Organic cation-templated self-assembly of 4,4′-bipy (4,4′-bipy = bpy) with [NH4]2MS2O2 (M = Mo, W) and CuX (X = Cl, NCS) in the present of 1,1-bis(pyridinium)methylene [bpm = 1,1′-bis(pyridinium)methylene] resulted in four novel neutral heterothiometallic cluster polymers based on tetranuclear [Mo/WOS3Cu3] unit: [MOS3Cu3Cl(μ-bpy)2·Sol]n (M = Mo, Sol = 1.3DMF·5.5H2O 1; M = W, Sol = 1.5DMF·8.2H2O 2), [MoOS3Cu3(NCS)(bpy)(μ-bpy)2·DMF]n (3), and [WOS3Cu3(NCS)(μ-bpy)2.5·3DMF]n (4). Polymer 1 or 2 crystallizes in the Fddd space group with a 2-fold interpenetrating (10,3)-b net, which presents a 3-connected 3D heterothiometallic polymer assembled with bidentate organic bridging ligands. Polymer 3 crystallizes in the space group P1 with a 2D noninterpenetrating network with (6,3) topology in which [MoOS3Cu3(bpy)] units are interconnected via three single or double Cu-μ-bpy-Cu bridges. Polymer 4 crystallizes in the space group C2/c with a (64 82) net, which displays the first self-interpenetrating network in heterothiometallic chemistry. All of these results confirm the ideal template effect and correct choice of bpm.
Co-reporter:Chunying Xu, Linke Li, Yinping Wang, Qianqian Guo, Xianjuan Wang, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2011 Volume 11(Issue 10) pp:4667-4675
Publication Date(Web):August 29, 2011
DOI:10.1021/cg200961a
To systematically explore the influence of aromatic polycarboxylate coligands on building high-dimensional Cd(II)-bmb (1,4-bis(2-methylbenzimidazol-1-ylmethyl) benzene) coordination polymers, we synthesized six coordination polymers, namely {[Cd(bmb)(o-phda)]·H2O}n (1), [Cd(bmb)0.5(m-phda)]n (2), [Cd(bmb)(p-phda)]n (3), [Cd(bmb)0.5(oba)]n (4), [Cd(bmb)(bpdc)]n (5), [Cd2(bmb)(bta)(mta)0.5]n (6), (H2phda = phenylenediacetic acid, H2oba =4,4′-oxybis(benzoic acid), H2bpdc = biphenyl-4,4′-dicarboxylic acid, H3bta =1,2,4-benzenetricarboxylic acid, and H2mta = 2-(methoxycabonyl)terephthalic acid) by varying aromatic polycarboxylate coligands. Structural analyses reveal that polymers 1–6 display diverse 3D frameworks and topologies, in which all of the N-donor ligands bmb exhibit trans-conformation but with different Ndonor···N–Csp3···Csp3 torsion angles. Polymer 1 shows a 3-fold interpenetrating dia array with a 4-connected 66 topology. Polymer 2 features a (3,4)-connected pillar-layered structure with (63)(65·8)-ins topology. Polymer 3 is a 4-connected framework with 66-dia topology and two types of meso-helical chains. Polymer 4 possesses a 2-fold interpenetrating 6-connected framework with (412·63)-pcu topology. The structure of polymer 5 is a 4-connected 5-fold interpenetrating architecture with 66-dia topology. Interestingly, in 6, part of bta3- anions are converted into a new ligand mta2- via in situ esterification reaction under solvothermal conditions. As a result, polymer 6 exhibits a scarce mixed-ligands framework with two O-donor and one N-donor ligands based on tetranuclear Cd(II) clusters. It is an 8-connected (36·418·53·6)-hex topology. A systematically structural comparison of these polymers indicates that the coordination modes of aromatic polycarboxylates along with the structural characteristics of the semirigid N-donor ligand bmb simultaneously play an important role in constructing the high-dimensional frameworks. Moreover, polymers 1–6 indicate high thermal stabilities and different photoluminescence behaviors in the solid state.
Co-reporter:Xianju Shi, Xinhai Zhang, Xiaoxia Li, Hongwei Hou, Yaoting Fan
Journal of Molecular Structure 2011 Volume 996(1–3) pp:110-114
Publication Date(Web):14 June 2011
DOI:10.1016/j.molstruc.2011.04.027
A microporous metal–organic framework {[Cu3Cl6(ttmb)4]·6H2O}n (1) (ttmb = 1,3,5-tris(1,2,4-triazol-1-ylmethyl)-benzene) with tetranodal (3,4)-connected topological type was prepared by the self-assembly reaction of the flexible tripodal ligand ttmb with CuCl2·2H2O. The ligand exhibits two infrequent coordination conformations in complex 1, and the framework has a large pore volume (remove the solvent molecules) of 1781.6 Å3 (36.3% of the total). The test of 1 as the catalyst in the oxidative coupling reaction of 2,6-dimethylphenol indicates that it is catalytically active by showing high conversion of DMP under the optimized reaction condition.Highlights► We synthesized a microporous metal–organic framework with a large pore volume. ► The tripodal ligand in complex 1 exhibits two infrequent coordination conformations. ► Complex 1 shows high catalytically active in the green oxidative coupling reaction of DMP.
Co-reporter:Chunying Xu, Xianjuan Wang, Degang Ding, Hongwei Hou, Yaoting Fan
Inorganic Chemistry Communications 2011 Volume 14(Issue 9) pp:1410-1413
Publication Date(Web):September 2011
DOI:10.1016/j.inoche.2011.05.034
In our efforts to tune structure by cation exchange reaction, a rare 1-D meso-helical chain [CdL(Ac)2]n (1) was immersed into the methanol solution of Hg(Ac)2, and then new crystals of {[HgL0.5(Ac)2]·(CH3OH)}n (2) (L = 1,4-bis(2-methylbenzimidazol-1-ylmethyl) benzene) were obtained on the surface of 1. Single crystal X-ray analysis reveals that complex 2 shows a 1-D zigzag chain, in which the mercury ion adopts an unprecedented six-coordinated mode in binuclear unit. Notably, the framework of 2 is completely different from that of 1. In addition, the determination of Scanning Electron Microscope and Energy-Dispersive X-ray Spectrometry reveals that the exchange is a recurrent dissolving-exchange-crystallization process of solvent-mediated mechanism. This work provides a new effective tactic of adjusting molecular structures.Through cation exchange reaction, a meso-helical Cd(II) chain has been adjusted to a zigzag Hg(II) chain with an unprecedented coordination mode. The results prove that the exchange is a recurrent dissolving-exchange-crystallization process of solvent-mediated mechanism by visual evidence. This work provides a new effective tactic of adjusting molecular structures.Research highlights► Tune structure from a meso-helical Cd(II) chain to a zigzag Hg(II) chain by cation exchange reaction. ► The exchange is a recurrent dissolving-exchange-crystallization process with a solvent-mediated mechanism. ► A new effective tactic of adjusting molecular structures.
Co-reporter:Yajuan Mu, Yajing Song, Chan Wang, Hongwei Hou, Yaoting Fan
Inorganica Chimica Acta 2011 Volume 365(Issue 1) pp:167-176
Publication Date(Web):15 January 2011
DOI:10.1016/j.ica.2010.09.001
Six novel Cd(II) coordination polymers based on 4,4′-bis(1,2,4-triazol-1-ylmethyl)biphenyl (btmb), namely, [Cd(btmb)2I2]n (1), [Cd(btmb)I2]n (2), {[Cd(btmb)2(NO3)2]·H2O}n (3), {[Cd(btmb)2(SCN)2]·3H2O}n (4), {[Cd(btmb)(CH3COO)2(H2O)]·CH3CN}n (5) and [Cd(btmb)Cl2(H2O)]n (6) have been synthesized by the reactions of btmb with Cd(II) salts in the presence of different anions (I−, NO3-, NCS−, CH3COO− or Cl−) under appropriate reaction conditions. The assemblies of btmb with CdI2 afford two different structures: two-dimensional (2D) rhombohedral grid layer network structure 1 and 2D layer structure 2 involved with one-dimensional (1D) linear cadmium chains. Treatment of btmb with Cd(NO3)2·4H2O gives rise to a 2D grid network structure 3 which is similar to 1. When the I− or NO3− anions were replaced by NCS−, CH3COO− or Cl−, different 1D coordination polymers 4–6 were obtained, respectively. Polymer 4 displays a 1D double-chain structure, while both polymers 5 and 6 show 1D zigzag chain structures. In addition, the luminescence measurements reveal that polymers 1–6 exhibit different fluorescent emissions in the solid-state at room temperature, which can be attributed to the various coordination environments of Cd(II), solvent molecules and different packing interactions in these polymers.Six novel Cd(II)-containing coordination polymers have been synthesized under appropriate reaction conditions. The structural diversities of the final products show that the reaction conditions and anions have important effects on the formation of coordination polymers. The fluorescence properties of the polymers are also investigated.
Co-reporter:Junhong Fu, Junxing Fu, Yajuan Mu, Yanhua Liu, Hongwei Hou, Yaoting Fan
Inorganic Chemistry Communications 2011 Volume 14(Issue 11) pp:1823-1826
Publication Date(Web):November 2011
DOI:10.1016/j.inoche.2011.08.018
When metal–organic coordination polymers [M2(SO4)(TTTMB)2(H2O)4]·H2BTEC·2H2O (M = Cd: 1, Zn: 2; TTTMB = 1,3,5-tris(triazol-1-ylmethyl)-2,4,6-trimethylbenzene, H4BTEC = 1,2,4,5-benzenetetracarboxylate acid) with two dimensional layers were suspended in Cu(NO3)2 aqueous solution, a metal–organic coordination polymer [Cu2(TTTMB)(BTEC)(μ-H2O)(H2O)4]·6H2O (3) with three dimensional nets would be obtained by solvent-mediated cation-exchange reaction. The direct reaction of TTTMB and H4BTEC with CuSO4 in the absence of 1 or 2 affords different crystal [Cu3(TTTMB)2(H2BTEC)3(H2O)3]·3H2O (4).Through cation-exchange reaction, a Cd(II) or Zn(II) metal-organic coordination polymer with two dimensional layers can transform to a Cu(II) metal-organic coordination polymer with three dimensional nets. Visual evidence indicates that the reaction is a process of solvent-mediated reaction.Highlights► The structural transformation is from 2D Cd(II) or Zn(II) layers to 3D Cu(II) nets. ► The direct reaction of TTTMB and H4BTEC with CuSO4 affords a different crystal.
Co-reporter:Ben-Lai Wu, Rui-Ying Wang, Hong-Yun Zhang, Hong-Wei Hou
Inorganica Chimica Acta 2011 Volume 375(Issue 1) pp:2-10
Publication Date(Web):1 September 2011
DOI:10.1016/j.ica.2011.05.029
Six new 1–3D coordination polymers of an unsymmetrical angular ligand 3-pyridin-4-ylbenzoate (L), namely, [Ni(L)2(C2H6O2)]n (1), [Cd(L)2(H2O)2]n·4H2O (2), [Zn2(OH)(L)3]n (3), [Fe2(OH)(L)3]n (4), [Ni(L)2(H2O)]n (5) and [Cd(L)2(H2O)]n (6) were hydro(solvo)thermally synthesized. They have abounding structure chemistry ranging from one-dimensional ribbons (1 and 2), and two-dimensional novel helical double-layered frameworks (3 and 4) to three-dimensional CdSO4-topological porous interpenetrating architectures with hydrophilic and hydrophobic channels regularly arraying (5 and 6). The labile conformations and coordination modes of ligand L, which were finely tuned by reaction conditions, perhaps play the key role in the construction of various architectures. Very interestingly, the slight difference in solvent system or temperature resulted in the distinct architectures of nickel(II) complexes 1 and 5 or cadmium(II) complexes 2 and 6. As expected, the unsymmetrical ligand L has a trend to construct metal-organic helixes as observed in 3 and 4. Thermogravimetric analysis of 5 shows the main framework retains stability until a higher temperature 379 °C. The 3D microporous network of 5 can slightly absorb for N2 and Ar. Compounds 2, 3 and 6 emit ligand-centered photoluminescence but with obviously different intensities owing to the structural diversities and coordinating water molecules.Graphical abstractSix new coordination polymers of an unsymmetrical angular ligand 3-pyridin-4-ylbenzoate were hydro(solvo)thermally synthesized. Their structures range from 1D ribbons, and 2D helical double-layered frameworks to 3D interpenetrating CdSO4-topological architectures, where the labile conformations and coordination modes of ligand L finely tuned by reaction conditions perhaps play the key role in the construction of various architectures.Highlights► Hydro(solvo)thermal syntheses of coordination polymers of 3-pyridin-4-ylbenzoic acid. ► Metal-organic frameworks tuned by ligand conformations. ► Novel metal-organic helical structures resulted from unsymmetrical angular ligand.
Co-reporter:Chunying Xu, Linke Li, Qianqian Guo, Hongwei Hou, Yaoting Fan
Inorganic Chemistry Communications 2011 Volume 14(Issue 8) pp:1204-1208
Publication Date(Web):August 2011
DOI:10.1016/j.inoche.2011.04.018
By controlling the hydrothermal reaction temperature, three coordination polymers with the same ingredients but different dimensional architectures from 3D to 2D and 1D have been obtained, namely, [Cd(bmb)(Hip)2]n (1), {[Cd(bmb)(ip)]·H2O}n (2), and [Cd(bmb)(ip)(CH3CH2OH)(H2O)]n (3) (bmb = (1,4-bis(2-methylbenzimidazol-1-ylmethyl) benzene); H2ip = 1,3-benzenedicarboxylic acid). A careful investigation of the structures discloses that temperature parameters have significant effects on the conformations and coordination modes of the ligands and enhanced temperature favors the formation of higher dimensional products. In addition, the thermal stabilities and photoluminescence properties of polymers 1–3 in the solid state have also been investigated.The dimensionality of Cd(II)/ip/bmb polymers have been adjusted from 3D self-penetrated pillared-layer framework to 2D grid-layer and 1D trapezoid-like chain by varying the hydrothermal reaction temperature. In addition, these polymers show high thermal stability and different fluorescent emissions.Research Highlights► Three coordination polymers with the same ingredients but different dimensional architectures from 3D to 2D and 1D. ► Temperature parameters have significant effects on the conformations and coordination modes of the ligands. ► Enhanced temperature favors the formation of higher dimensional products.
Co-reporter:Zhong-Ming Gu;Qing-Li Wang;Yun-Yin Niu
Journal of Chemical Crystallography 2011 Volume 41( Issue 4) pp:533-536
Publication Date(Web):2011 April
DOI:10.1007/s10870-010-9915-3
A new coordination polymer based on Group IB metal thiocyanates, [Ag2I (NCS)2(dpds)2]n (1) (dpds = 2,2′-dipyridyldisulfide), has been synthesized by the pre-assembly method and characterized by X-ray crystallography. In 1, the AgI center adopts tetrahedral coordination geometry and the 2-D undulated layers of (4, 4) topology network is formed by dpds ligand with zigzag NCS−Ag chains.
Co-reporter:Shengli Huang, Xiaoxia Li, Xianju Shi, Hongwei Hou and Yaoting Fan
Journal of Materials Chemistry A 2010 vol. 20(Issue 27) pp:5695-5699
Publication Date(Web):10 Jun 2010
DOI:10.1039/C0JM00605J
Using 2D grids of [Cd(btx)2Cl2]n1 and [Co(btx)2Cl2]n2 (btx = 1,4-bis(triazol-1-ylmethyl)benzene) as parent complexes, with terminal dicarboxylic ions as anion substitutors and bridge ligands, we synthesized extended structures of 3D polymeric networks with {[Cd2(btx)2(tp)2]·H2O}n3 and [Co3(btx)4(tp)3(H2O)4]n4 (tp = terephthalic ion) with Schläfli symbols (423·65) and (44·62)(48·67), respectively. The complete cation exchanged products Cu2+-1, Cu2+-3 and Cd2+-4 were obtained by immersing 1, 3 and 4 into corresponding aqueous solutions of MCl2 (M = Cu2+ or Cd2+). Interestingly, fluorescence studies on the pre- and post-exchanged materials compounds indicate that central metal ions have great influence on the fluorescence signal of the materials compounds, and play more important roles than skeleton structures.
Co-reporter:Jiyong Hu ; Jin’an Zhao ; Qianqian Guo ; Hongwei Hou ;Yaoting Fan
Inorganic Chemistry 2010 Volume 49(Issue 8) pp:3679-3681
Publication Date(Web):March 15, 2010
DOI:10.1021/ic902450c
An unprecedented high-nuclearity metallamacrocycle-based 3D silver framework with formula {[Ag2(C25H27N6O)2](CH3OH)(H2O)0.17}n (1), built on the basis of dodecanuclear silver building blocks, has been synthesized and characterized, and it shows strong phosphorescence emission at 10 K, which is a consequence of the presence of intersystem crossing from singlet to triplet caused by the heavy-atom effect of silver ions.
Co-reporter:Xianju Shi, Xia Wang, Linke Li, Hongwei Hou and Yaoting Fan
Crystal Growth & Design 2010 Volume 10(Issue 6) pp:2490
Publication Date(Web):May 5, 2010
DOI:10.1021/cg900566v
To investigate the influence of spatial extended direction and flexibility of secondary ligand on the resulting structure, eight new ferrocene-containing complexes with various dimensionalities have been synthesized by the reactions of CdII salts and 1,1′-bis(3-carboxy-1-oxopropyl)ferrocene (H2bfcs) with series of rationally selected N-heterocyclic spacers. When the small organic molecule 4-aminopyridine (apy) was employed as a secondary ligand, a one-dimensional (1D) linear complex {[Cd(bfcs)(apy)2]·H2O}n (1) was furnished, while the use of bis(azole) bridging ligands resulted in the formation of a 1D ribbon complex {[Cd(bfcs)(bbbm)1.5]·CH3OH·2H2O}n (2), a rare 1D quadruple-chain complex {[Cd(bfcs)(btmb)]·3H2O}n (3) and two two-dimensional (2D) puckered complexes {[Cd2(bfcs)2(pbbm)2]·2H2O}n (4) and {[Cd(bfcs)(bix)]·H2O}n (5) (bbbm = 1,1′-(1,4-butanediyl)bis-1H-benzimidazole, btmb = 4,4′-bis(1,2,4-triazole-1-ylmethyl)biphenyl, pbbm = 1,1′-(1,3-propanediyl)bis-1H-benzimidazole, bix = 1,4-bis(imidazole-1 -ylmethyl)benzene). In addition, the tripodal bridging secondary ligand led to an unusual three-dimensional (3D) layer pillar complex {[Cd2(bfcs)(titb)2Cl2]·2CH3OH·4H2O}n (6) (titb =1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene). Employment of a flexible multidentate molecule tris(2-benzimidazolylmethyl)amine (ntb) as the secondary ligand gave birth to a mononuclear complex [Cd(bfcs)(ntb)]·DMF·5H2O (7) and a binuclear complex [Cd2(bfcs)(ntb)2]·bfcs·5H2O (8), in which ntb adopted the chelating coordination mode. It can be observed from the coordination architectures of 1−8 that secondary ligands had great effects on the spatial connective fashions of CdII centers, resulting in the formation of various dimensional complexes.
Co-reporter:Fangfang Pan, Jie Wu, Hongwei Hou and Yaoting Fan
Crystal Growth & Design 2010 Volume 10(Issue 9) pp:3835-3837
Publication Date(Web):July 21, 2010
DOI:10.1021/cg1002868
When a well-designed tetranuclear NiII cage [Ni4(bppdca)2(H2bppdca)4(SO4)2(H2O)6]·H2O·CH3OH (1; H2bppdca = N,N′-bis(pyridin-3-yl)-2,6-pyridinedicarbox-amide) was immersed into the methanol solution of CuSO4, a novel decanuclear CuII complex [Cu10(H2bppdca)4(SO4)8(μ3OH)4(CH3OH)(H2O)4]·11H2O·2CH3OH (2) would be obtained through central metals transformation. We propose that the transformation is a recurrent dissolving−exchange−crystallization process with a solvent-mediated mechanism confirmed by visual evidence. Direct reaction of H2bppdca and CuSO4 in the absence of 1 affords different products.
Co-reporter:Xianju Shi;Weiyin Wang;Hongwei Hou ;Yaoting Fan
European Journal of Inorganic Chemistry 2010 Volume 2010( Issue 23) pp:3652-3657
Publication Date(Web):
DOI:10.1002/ejic.201000395
Abstract
Reaction of a flexible tripodal ligand, 1,3,5-tris(1,2,4-triazol-1-ylmethyl)-2,4,6-trimethylbenzene (tttmb), and an organometallic carboxylate 1,1′-bis(3-carboxy-1-oxopropyl)ferrocene (H2bfcs) with Cd(Ac)2·2H2O yields a trinodal, self-catenated 3D layer pillar complex {[Cd3(bfcs)3(tttmb)2(H2O)4]·8H2O}n (1), which is formed by connecting 2D hexagonal CdII–tttmb Borromean layers through ferrocenyl bridges in both inter- and intralayers. The complex can undergo a dehydrated and rehydrated process in a single-crystal-to-single-crystal manner without affecting the overall framework. The amorphous sample of 1 can be regenerated by water to the crystalline material again. In addition, the nitrogen adsorption property of 1 was also investigated.
Co-reporter:Jinpeng Li, Zhijia Song, Huijuan Lü, Yong Hou, Hongwei Hou, Yaoting Fan
Inorganic Chemistry Communications 2010 Volume 13(Issue 3) pp:436-439
Publication Date(Web):March 2010
DOI:10.1016/j.inoche.2010.01.006
Through substituation reaction, one lead ferroceneyl carboxylate polymer, namely [Pb(μ2-OOCClH3C6Fc)2(phen)]n1a [Fc = (η5-C5H5)Fe(η5-C5H4)] was synthesized from precursor [Pb(μ2-η2-OOCClH3C6Fc)2(CH3OH)2]n1. However, a mononuclear Pb(II) complex {[Pb(η2-OOCClH3C6Fc)2(phen)]·(CH3OH)·(H2O)} 2 could be obtained from the traditional one-pot reaction of FcC6H3ClCOONa and Pb(OAc)2 with 1,10-phenantholine (phen). The electrochemical studies of 1, 1a, 2 and FcC6H3ClCOOH indicate that the half-wave potentials of the ferrocenyl moieties in these complexes are all shifted to positive potential compared with that of FcC6H3ClCOOH.The substitution reaction of 1-D precursor [Pb(μ2-η2-OOCClH3C6Fc)2(CH3OH)2]n1 with phen results in one 1-D polymer[Pb(μ2-OOCClH3C6Fc)2(phen)]n1a. However, a mononuclear Pb(II) complex {[Pb(η2-OOCClH3C6Fc)2(phen)]·(CH3OH)·(H2O)} 2 could be obtained from the traditional one-pot reaction. The structural integrity of precursor can be maintained in the resultant polymer. Their electrochemistry properties are also investigated.
Co-reporter:Ben-Lai Wu, Rui-Ying Wang, E. Ye, Hong-Yun Zhang, Hong-Wei Hou
Inorganic Chemistry Communications 2010 Volume 13(Issue 1) pp:157-159
Publication Date(Web):January 2010
DOI:10.1016/j.inoche.2009.10.040
Co-reporter:Likun Duan, Yanan Ding, Xiangru Meng, Weiqiang Li, Hongwei Hou, Yaoting Fan
Journal of Molecular Structure 2010 Volume 975(1–3) pp:53-58
Publication Date(Web):30 June 2010
DOI:10.1016/j.molstruc.2010.03.078
Three new complexes with the formulas [Cd(bmi)2I2] (1), [Cd(bmi)2(Cl)2]n (2) and [Cd(bmi)2(SCN)2]n (3) have been obtained through the self-assembly of an unsymmetrical ligand 1-((benzotriazol-1-yl)methyl)-1-H-1,3-imidazole (bmi) with Cd(II) salts at room temperature. Single crystal X-ray diffraction determination shows that complex 1 possesses mononuclear structure, complex 2 displays 1-D chain structure constructed by chloride bridging Cd(II) ions, and complex 3 exhibits 2-D grid network structure. In complexes 1 and 2, the unsymmetrical bmi ligands coordinate to metal ions as monodentate mode with the N atom from imidazole ring in preference to the N atom from benzotriazol ring. While in complex 3, bmi ligands coordinate to metal ions as μ2-bridging mode with N atoms from imidazole and benzotriazol rings simultaneously. Additionally, their fluorescent properties also have been determined.
Co-reporter:Yajuan Mu, Jie Yang, Shuang Han, Hongwei Hou, Yaoting Fan
Materials Letters 2010 Volume 64(Issue 11) pp:1287-1290
Publication Date(Web):15 June 2010
DOI:10.1016/j.matlet.2010.03.010
The rod-like and dandelion-like CuO nanomaterials have been prepared by the decomposition of a copper complex [Cu(pbbt)Cl2]2·CH3OH (pbbt = 1,1′-(1,3-propylene)-bis-1H-benzotriazole) in the presence of suitable surfactants and alkalies under hydrothermal conditions. The CuO nanorods are about 50 nm in diameter and up to 500–700 nm in length; the average diameter of the dandelion-like CuO microspheres is of 2 μm. A formation mechanism for the CuO nanomaterial was proposed. The gas-sensing properties of as-prepared CuO nanomaterial were studied. The sensitivity of the as-prepared CuO nanorods was better than that of dandelion-like CuO particles, and the CuO nanorods displayed special sensitivity to alcohol.
Co-reporter:Jin’an Zhao, Jie Wu, Jiyong Hu, Hongwei Hou, Yaoting Fan
Inorganica Chimica Acta 2010 Volume 363(Issue 4) pp:662-668
Publication Date(Web):1 March 2010
DOI:10.1016/j.ica.2009.11.017
Co-reporter:Yushan Chang, Hong Xu, Shaopei Xie, Jinpeng Li, Xuling Xue, Hongwei Hou
Inorganic Chemistry Communications 2010 Volume 13(Issue 8) pp:959-963
Publication Date(Web):August 2010
DOI:10.1016/j.inoche.2010.05.006
The reactions of semi-rigid bidentate ligand 4,4′-bis(benzimidazol-1-ylmethyl)biphenyl (bbmb) with NiCl2 and CuCl2 and Cd(OAc)2 afford novel complexes {[M(bbmb)2(Cl)(OH)](H2O)2}n (M = Ni(1), Cu(2)) and [Cd2(OAc)4(bbmb)3]2(CH3OH)3(H2O)2 (3). Both complexes 1 and 2 feature parallel 2-fold interpenetrating (4,4)-windmill-like layer morphology. Complex 3 presents unique discrete quad-nuclear motif comprised by two couples of alternating single and double twisting chains. The three complexes exhibit active second-order NLO effects.The reactions of rigid 4,4′-bis(benzimidazol-1-ylmethyl)biphenyl (bbmb) with NiCl2 and CuCl2 and Cd(OAc)2 afford novel complexes {[M(bbmb)2(Cl)(OH)](H2O)2}n (M = Ni(1), Cu(2)) and [Cd2(OAc)4(bbmb)3]2(CH3OH)3(H2O)2 (3). Both complexes 1 and 2 feature parallel 2-fold interpenetrating (4,4)-windmill-like layer morphology. Complex 3 presents unique discrete quad-nuclear motif comprised by two couples of alternating single and double twisting chains. The three complexes exhibit active second-order NLO effects.
Co-reporter:Shuangliang Liu, Yu Yang, Yongfang Qi, Xiangru Meng, Hongwei Hou
Journal of Molecular Structure 2010 Volume 975(1–3) pp:154-159
Publication Date(Web):30 June 2010
DOI:10.1016/j.molstruc.2010.04.013
Self-assemblies of Cd(II) or Zn(II) salts with hybrid ligands sodium 4-ferrocenylbutyrate and 1,1-(1,4-butanediyl)bis-1H-benzimidazole (bbbm) gave rise to two new coordination polymers {[Cd(η2-OOC(CH2)3Fc)2(bbbm)]·CH3OH}n (1) and {[Zn(OOC(CH2)3Fc)(η2-OOC(CH2)3Fc)(bbbm)]·CH3OH}n (2) (Fc = (η5-C5H5)Fe(η5-C5H4)). Both polymers possess 1D helical chain structures with 21 screw axes along the b-direction although the coordination modes of the 4-ferrocenylbutyrate ligands and the coordination environments of the central metals in the two polymers are different. In addition, the redox properties of polymers 1 and 2 are also investigated and the results show that the formal potentials and the self-diffusion coefficients of the two polymers are close to each other.
Co-reporter:Linke Li, Hong Xu, Xianju Shi, Hongwei Hou, Yaoting Fan
Inorganica Chimica Acta 2010 Volume 363(Issue 14) pp:3939-3944
Publication Date(Web):25 November 2010
DOI:10.1016/j.ica.2010.07.063
Using the pyridine dicarboxamide derivative N,N′-bis(1,3,4-thiadiazol-2-yl)-2,6-pyridinedi-carboxamide (H2-btapca) as ligand, two novel polynuclear complexes: dimeric {[Cu2(μ2-O2H)(btapca)2]·DMF·H2O} (1) and tetrameric {[Ni4((μ2-O2H)2(btapca)4)]·DMF·MeOH·3.5H2O} (2) were obtained. In complex 1, two center Cu(II) ions are bounded by two btapca ligands and one aqueous molecule acting as a μ2-H2O bridge connect them together. Complex 2 is a tetrameric complex, in which the based backbone is an assumed Ni4 tetrahedron with two μ2-O2H bridges existing inside the tetrahedron forming a basic [Ni2(μ2-O2H)]2 core, which are surrounded by four btapca ligands. The magnetic properties of the two polynuclear complexes were determined, the results show that for both of the two complexes, the overall weak ferromagnetic exchange interactions between central metal ions are evident, the best fitting parameters are: J = 7.47 cm−1 (g = 2.21) for dimeric Cu(II) complex 1, and 2J1 = 4.8 cm−1, 2J2 = −0.00204 cm−1(g = 2.14, zJ′ = 0.00077 cm−1) for tetrameric Ni(II) complex 2.Based on a pyridine dicarboxamide ligand, two polynuclear complexes: dimeric {[Cu2(μ2-O2H)(btapca)2]·DMF·H2O} (1) and tetrameric {[Ni4((μ2-O2H)2 (btapca)4)]·DMF·MeOH·3.5H2O} (2) were obtained. In these complexes, aqueous molecules acting as μ2-H2O bridge connect the adjacent metal ions together. The magnetic properties investigations show that both of the two complexes display overall ferromagnetic exchange interactions between the metal centers.
Co-reporter:Xiangru Meng, Wan Zhou, Yongfang Qi, Hongwei Hou, Yaoting Fan
Journal of Organometallic Chemistry 2010 695(5) pp: 766-774
Publication Date(Web):
DOI:10.1016/j.jorganchem.2009.12.015
Co-reporter:HuiJun Li;ErPeng Zhang;QianQian Guo;HongWei Hou;YaoTing Fan
Science China Chemistry 2010 Volume 53( Issue 10) pp:2118-2122
Publication Date(Web):2010 October
DOI:10.1007/s11426-010-4110-0
A porous three-dimensional copper(II) metal-organic framework (MOF) {[Cu2(tci)(OH)(pip)0.5(H2O)]·6H2O}n (1) [tci = tris (2-carboxyethyl)isocyanurate, pip = piperazine] has been generated under hydrothermal conditions at 120 °C. Single crystal X-ray diffraction reveals that the polymer exhibits a novel three-dimensional framework based on planar tetranuclear copper(II) cluster units. The variable temperature magnetic susceptibility data in the range 2–280 K show antiferromagnetic spin-spin coupling in the tetranuclear unit in complex 1. A theoretical fitting of the magnetic data gives J values of −31.3 cm−1, −30.8 cm−1, and 13.5 cm−1.
Co-reporter:Xiang-Ru Meng, Xin-Juan Wu, Da-Wei Li, Hong-Wei Hou, Yao-Ting Fan
Polyhedron 2010 29(13) pp: 2619-2628
Publication Date(Web):
DOI:10.1016/j.poly.2010.06.009
Co-reporter:Erpeng Zhang, Hongwei Hou, Xiangru Meng, Yaru Liu, Yun Liu and Yaoting Fan
Crystal Growth & Design 2009 Volume 9(Issue 2) pp:903
Publication Date(Web):December 2, 2008
DOI:10.1021/cg800661g
Seven ferrocenyl functional coordination polymers with the formulas [Zn2(μ2-O2CRFc)4(4,4′-bpy)]n [(R = (CH2)m with m = 0 (1), 1 (2), 2 (3), 3 (4)], [Zn(O2C(CH2)4Fc)2(H2O)2(4,4′-bpy)]n (5), [Zn2Ca(μ2-O2CCH2Fc)6·Zn2(μ2-O2CCH2Fc)4(4,4′-bpy)2]n (6) and [Zn2Ca(μ2-O2C(CH2)2Fc)6(4,4′-bpy)]n (7) (Fc = ferrocene) have been synthesized and characterized. Single-crystal X-ray diffraction studies reveal that their one-dimensional (1-D) chain structures consist of various organometallic building blocks held together by 4,4′-bpy linkers. Polymers 1−4 are based on the paddle-wheel binuclear motif [Zn2(O2CRFc)4]. Polymer 5 is built from the mononuclear unit [Zn(O2CRFc)2(H2O)2]. Polymer 7 is assembled by the linear heterotrinuclear cluster [Zn2Ca(O2CRFc)6] which has been rarely reported up to now. The structure of polymer 6 is a particularly fascinating 1-D chain in which two kinds of building blocks ([Zn2(O2CRFc)4] and [Zn2Ca(O2CRFc)6]) are connected alternately by 4,4′-bpy linkers. These results demonstrate that the total numbers of incorporated ferrocene moieties as well as the structures of 1−7 are closely related to the variation of metal nuclearity (from mononuclear to trinuclear) of the three kinds of organometallic building blocks. The electrochemical studies reveal a good correlation between the Fc/Fc+ redox potentials of 1−7 and the number of methylene in ferrocenyl carboxylates.
Co-reporter:Jinpeng Li, Linke Li, Hongwei Hou, and Yaoting Fan
Crystal Growth & Design 2009 Volume 9(Issue 10) pp:4504
Publication Date(Web):August 7, 2009
DOI:10.1021/cg9005218
In this paper, the reaction of polymeric zinc ferrocenyl carboxylate, {[Zn(OOCClH3C6Fc)2(H2O)3](CH3OH)}n (1; FcC6H3ClCOONa = sodium 2-chloro-4-ferrocenylbenzoic), with Pb(NO3)2 or Cd(NO3)2 was investigated. By immersion of selected big single crystals of 1 into aqueous solutions of Pb(NO3)2 and Cd(NO3)2, respectively, two central metal ion exchange induced single-crystal to single-crystal (SCTSC) transformation products, {[Zn0.74Pb0.26(OOCClH3C6Fc)2(H2O)3](H2O)}n (2) and {[Zn0.82Cd0.18(OOCClH3C6Fc)2(H2O)3](H2O)}n (3), could be obtained. In contrast to above-mentioned SCTSC products, 1 can dissolve well in THF solution, and the reaction of the solution containing 1 with Pb(NO3)2 or Cd(NO3)2 results in a 1-D Pb(II) polymer, [Pb(μ2-η2-OOCClH3C6Fc)2(CH3OH)2]n (4), and a mononuclear Cd(II) complex, {[Cd(η2-OOCClH3C6Fc)2(H2O)3](CH3OH)2} (5). Our results indicate that metal ion exchange can be implemented through heterogeneous or homogeneous pathways and suggest an easy means to remove lead and cadmium ions. At the same time, it also set the stage for using analogous metal carboxylates for selective exchange of other cations.
Co-reporter:Jie Wu;Hong-Wei Hou;Yue-Xin Guo;Yao-Ting Fan ;Xia Wang
European Journal of Inorganic Chemistry 2009 Volume 2009( Issue 19) pp:2796-2803
Publication Date(Web):
DOI:10.1002/ejic.200900058
Abstract
Reaction of a rigid conjugated clamp-like multi-pyridineligand N,N′-bis(pyridin-3-yl)-2,6-pyridinedicarboxamide (H2L) with CuSO4·5H2O or Cu(OAc)2 resulted in the formation of two high-nuclearity, discrete molecular copper(II) complexes, namely [Cu10(H2L)5(SO4)8(μ3-OH)4(H2O)2]·4CH3CH2OH·7H2O (1) and [Cu6(L)4(CH3COO)4]·2DMF·6H2O (2). In 1, ten copper atoms are engaged by five H2L ligands, eight SO42– and four μ3-OH groups to form a novel decanuclear copper complex which sits on a crystallographic twofold axis passing through the centre of the complex. The structure of 2 features a hexanuclear copper cage and a crystallographic centre of inversion is at the mid-point of the compound. The rigid conjugated clamp-like H2L ligands, polydentate in nature, form a “coordination pocket” arising from their “arms” to entrap the copper atoms and play an important role in the assembly of discrete molecular high-nuclearity complexes 1 and 2. Applications of 1 and 2 as heterogeneous catalysts for the oxidative polymerisation of 2,6-dimethylphenol showed very promising results at ambient temperature and these novel catalytic systems are very mild, efficient, regioselective and easily recyclable. The interesting catalytic properties of 1 and 2 can be attributed to their particular structural characteristics and their unusual reactivities based on cooperativity or electron transfer between multicopper centres. Magnetic studies of these copper(II) cages indicate antiferromagnetic behaviour. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Co-reporter:Haiyan Yang, Hongwei Hou, Yaoting Fan
Inorganica Chimica Acta 2009 Volume 362(Issue 7) pp:2418-2422
Publication Date(Web):15 May 2009
DOI:10.1016/j.ica.2008.10.031
Two one-dimensional metal–organic complexes containing ferrocenylthiocarboxylate components, [M(η2-SOCFc)2(btx)]n (M = Ni, 1, Co, 2; Fc = (η5-C5H5)Fe(η5-C5H4); btx = 1,4-bis(triazol-1-ylmethyl)benzene), have been synthesized and structurally characterized. X-ray crystal structural analyses reveal that the two complexes are isomorphous. Both of them exhibit interesting topological motif: 1-D sine curve chain structure. Photoluminescent studies suggest that the two complexes and the ligand FcCOSNa all exhibit broad fluorescence signals with the emission maxima at approximately 390 nm. Electrochemical studies show that the half-wave potentials of the ferrocenyl moieties in 1 and 2 have deviations relative to the free FcCOSNa ligand. Additionally, using quantum chemistry calculations, we further analyzed their luminescent and electrochemical behaviors.Two one-dimensional metal–organic complexes containing ferrocenylthiocarboxylate components have been synthesized and structurally characterized. The isostructural complexes 1 and 2 exhibit interesting topological motif: 1-D sine curve chain structure. We investigated their photoluminescent and electrochemical properties and further analyzed these properties by quantum chemistry calculations.
Co-reporter:Linke Li, Xiaohui Li, Hongwei Hou, Yaoting Fan
Inorganica Chimica Acta 2009 Volume 362(Issue 2) pp:599-604
Publication Date(Web):20 January 2009
DOI:10.1016/j.ica.2008.04.010
Two complexes containing o-ferrocenylbenzoate [o-−OOCH4C6Fc, Fc = (η5-C5H5)Fe(η5-C5H4)] components: {[Pb(η2-o-OOCH4C6Fc)2(phen)](NO3)} (phen = phenanthroline) (1) and {[Zn(η2-o-OOCH4C6Fc)2(bpe)](CH3OH)}n (bpe = 1,2-bis(4-pyridyl) ethene) (2) have been synthesized and structurally characterized by single crystal X-ray diffraction. 1 gives a discrete mononuclear framework, 2 features an infinite 1-D chain structure constructed by the bpe linking two adjacent zinc (II) ions. The third-order nonlinear optical (NLO) properties of complexes 1, 2 and the reactant o-NaOOCH4C6Fc were determined by Z-scan techniques in DMF solution. The results show that the structures of complexes have great impact on NLO properties. Complex 1 and o-NaOOCH4C6Fc display self-defocusing behaviors, while complex 2 exhibits strong self-focusing effect. The solution-state differential pulse voltammograms of complexes 1, 2 and o-NaOOCH4C6Fc were investigated as well. The results reveal that the half-wave potential of the ferrocenyl moieties is strongly influenced by the Pb(II) or Zn(II) ions in complexes 1 and 2.Two o-ferrocenylbenzoate based complexes {[Pb(η2-o-OOCH4C6Fc)2(phen)](NO3)} (1) and {[Zn(η2-o-OOCH4C6Fc)2(bpe)](CH3OH)}n (2) have been synthesized and structurally characterized by single crystal X-ray diffraction. Complex 1 gives a discrete mononuclear framework, 2 features an infinite 1-D chain structure constructed by the bpe linking two adjacent zinc (II) ions. Determination of the third-order NLO properties of complexes 1, 2 and o-NaOOCH4C6Fc shows that the structures of complexes have a significant effect on the NLO properties. In addition, their electrochemical properties were also investigated.
Co-reporter:Xiao-Rui Lv, Fu-Kai Zhao, Xiao-Ling Guo, Yun-Yin Niu, Na Xu, Hong-Wei Hou, Yao-Ting Fan, Dong Sun, Yu Zhu
Inorganic Chemistry Communications 2009 Volume 12(Issue 7) pp:653-656
Publication Date(Web):July 2009
DOI:10.1016/j.inoche.2009.05.014
Co-reporter:Hong Xu, Ying Lin Song, Xiang Ru Meng, Hong Wei Hou, Ming Sheng Tang, Yao Ting Fan
Chemical Physics 2009 Volume 359(1–3) pp:101-110
Publication Date(Web):18 May 2009
DOI:10.1016/j.chemphys.2009.03.011
Abstract
Two Ag(I)-bridged metal-organic polymers: 2D double-crossed layer polymer {[Ag(bpfp)] · NO3 · H2O)}n (bpfp = N,N′-bis(3-pyridylformyl)-piperazine) (1) and 1D zigzag chain polymer {[Ag(btx)] · NO3}n (btx = 1,4-bis(triazol-1-ylmethyl)-benzene) (2) have been prepared and structurally characterized by single crystal diffraction. Their third-order nonlinear optical (NLO) properties and optical limiting (OL) effects were determined by Z-scan technique. The results show that both polymers possess strong optical nonlinear absorption and optical nonlinear refraction, and exhibit strong OL effect to nanosecond and picosecond incident pulsed laser. By comparing the optical nonlinearities of the polymers and purely bpfp and btx ligands, we find that the incorporation of Ag ion can largely enhance the optical nonlinearities of organic molecules attached. DFT calculation further confirms the corporate contributions of Ag ions and bridge ligands to the optical nonlinearities.
Co-reporter:Xianju Shi, Hongwei Hou, Liwei Mi, Yali Sang, Yaoting Fan, Ruoyi Liu
Inorganica Chimica Acta 2009 Volume 362(Issue 9) pp:3364-3372
Publication Date(Web):1 July 2009
DOI:10.1016/j.ica.2009.03.018
Co-reporter:Jiyong Hu, Jinpeng Li, Jin’an Zhao, Hongwei Hou, Yaoting Fan
Inorganica Chimica Acta 2009 Volume 362(Issue 14) pp:5023-5030
Publication Date(Web):10 November 2009
DOI:10.1016/j.ica.2009.08.009
To investigate the effect of organic anions on the coordination frameworks, we synthesized five new complexes, namely, {[Zn3(μ-OH2)2(btc)2(btx)3]·4H2O}n (1), [Zn(bdc)(btx)]n (2), {[Ag8(3,5-pydc)4(btx)4]·8H2O}n (3), [Ag(2,6-Hpydc)(btx)]n (4) and [Cd2(μ2-OH2)(2,6-pydc)2(btx)]n (5) (H2bdc = 1,4-benzenedicarboxylic acid; H3btc = 1,3,5-benzenetricarboxylate; 3,5-H2pydc = pyridine-3,5-dicarboxylic acid; 2,6-H2pydc = pyridine-2,6-dicarboxylic acid), which were obtained by the reactions of 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (btx) as main ligand, and several aromatic polycarboxylate as organic anions with different d10 metal salts. Single crystal structure analysis shows that complexes 1, 3 and 5 possess 3D structures, 2 takes a 2D layer motif, and 4 displays a 1D chain structure. The distinct structures indicate that polycarboxylate anions with the diverse coordination modes and coordination groups can affect the topologies of metal–organic frameworks. In addition, the luminescence measurements reveal that the complexes 1, 2 and 5 exhibit strong fluorescent emissions in the solid state at room temperature.To investigate the effect of organic anions on the coordination frameworks, five new complexes were obtained. The distinct structures indicate that polycarboxylate anions with the diverse coordination modes and coordination groups can affect the topologies of metal–organic frameworks.
Co-reporter:Xiangru Meng, Yun Liu, Hongwei Hou, Yaoting Fan
Journal of Molecular Structure 2009 Volume 933(1–3) pp:163-168
Publication Date(Web):17 September 2009
DOI:10.1016/j.molstruc.2009.06.025
Three new complexes, [Co(OOC(CH2)4Fc)2(4,4′-bipy)(H2O)2]n (1), [Cd(OOC(CH2)4Fc)2(4,4′-bipy)(H2O)2]n (2), and {[Co(η2-OOC(CH2)4Fc)2(bbbm)]·(CH3OH)}n (3) [bbbm = 1,1′-(1,4-butanediyl)bis-1H-benzimidazole, Fc = (η5-C5H4)Fe(η5-C5H4)], were obtained from the corresponding metal salts with the primary ligand 5-ferrocenylpentanoic acid and the subsidiary N-heterocyclic ligands, and their structures were fully characterized. X-ray diffraction analyses reveal that all of the complexes display 1-D chain structure and complexes 1 and 2 are isostructural. The electrochemical properties of complexes 1–3 and 5-ferrocenylpentanoic acid have been investigated in DMF solution. The results show that the half-wave redox potentials of the three complexes are close to the 5-ferrocenylpentanoic acid, which indicates that the coordination of the metal ions does not have significant effects on the redox potential of the 5-ferrocenylpentanoic acid ligand. Further investigations suggest that the redox processes of 5-ferrocenylpentanoic acid and complexes 1–3 are all chemically quasi-reversible processes and controlled by diffusion.
Co-reporter:Xiangru Meng, Xiaoqing Zhu, Yongfang Qi, Hongwei Hou, Yaoting Fan
Journal of Molecular Structure 2009 Volume 934(1–3) pp:28-36
Publication Date(Web):30 September 2009
DOI:10.1016/j.molstruc.2009.06.015
The main aim of the work herein presented is to investigate the influence of different anions on the structures of a series of complexes. Through the self-assembly of a new unsymmetrical ligand 1-((benzotriazol-yl)methyl)-1H-1,3-imidazole (bmi) with M(NO3)2 or MSO4 [M = Zn(II), Co(II), Cd(II), Cu(II)], a series of new complexes, [M(bmi)2(NO3)2]n [M = Zn (1), Co (2), Cd (3), Cu (4)] and [M(bmi)(H2O)4(SO4)]·2H2O [M = Zn (5), Co (6), Cd (7), Cu (8)], have been synthesized. X-ray diffraction analyses revealed that the bmi ligands coordinate to the central metal ions with bridging bidentate mode leading to polynuclear isostructural complexes (1–4) in the reactions of nitrates with bmi. While in the reactions of sulfates with bmi, the bmi ligands coordinate to the central metal ions with a simple monodentate mode resulting in isostructural mononuclear complexes (5–8). These results suggest that the change of anion can influence the coordination modes of the ligand, and then influence the structures of the complexes. The thermal analysis studies indicate that nitrate-containing complexes 1–4 are more stable than the sulfate-containing complexes 5–8.
Co-reporter:Jie Wu, Fangfang Pan, Hongwei Hou, Jin’an Zhao, Yaofei Zhao, Yaoting Fan
Inorganic Chemistry Communications 2009 Volume 12(Issue 8) pp:750-754
Publication Date(Web):August 2009
DOI:10.1016/j.inoche.2009.06.006
Reaction of a rigid conjugated clamp-like ligand N,N′-bis(pyridin-3-yl)-2,6-pyridinedicarboxamide (bppdca) with ZnSO4·7H2O or CoSO4·7H2O resulted in the formation of two new polymers, namely, {[Zn2(bppdca)(SO4)2(DMF)2]·(DMF)}n (1) and {[Co(bppdca)(SO4)(CH3OH)(DMF)]·H2O}n (2). Both 1 and 2 feature one-dimensional double-chain structures with macrocyclic subunits, and the chains further self-assemble into a higher-dimensional framework via the hydrogen-bonding and π–π stacking interactions. Fluorescence studies show that the free ligand displays a strong fluorescence emission in solid state at room temperature, but in 1 and 2, the complexation of the ligand with metal ions and weak intermolecular interactions make the fluorescence emission partial quenching.Reaction of a rigid clamp-like ligand N,N′-bis(pyridin-3-yl)-2,6-pyridinedicarboxamide (bppdca) with ZnSO4·7H2O or CoSO4·7H2O resulted in two new polymers, namely, {[Zn2(bppdca)(SO4)2(DMF)2]·DMF}n (1) and {[Co(bppdca)(SO4)(CH3OH)(DMF)]·H2O}n (2). Single-crystal X-ray diffraction reveals that both structures were one-dimensional double chain connected by weak interactions generating higher dimension with macrocycles. Their fluorescence properties were reported in this article.
Co-reporter:Xiangru Meng, Sizeng Jin, Hongwei Hou, Chenxia Du, Seik Weng Ng
Inorganica Chimica Acta 2009 Volume 362(Issue 5) pp:1519-1527
Publication Date(Web):1 April 2009
DOI:10.1016/j.ica.2008.07.027
The computed results of the free bmt ligand reveal that the Mulliken charges of N18 and N23 are −0.391 and −0.275, respectively, and both of them have higher distributions in the highest occupied molecular orbital (HOMO) of the free ligand bmt. Based on the above results, four new complexes, [Cu(bmt)4] · (Cl)2 · 4H2O (1), [Cu(bmt)2(NCS)2] (2), [Cu(bmt)Cl]n (3), and [Ag(bmt)(NO3)]n (4) [bmt = 1-((benzotriazol-1-yl)methyl)-1-H-1,2,4-triazole], have been synthesized and characterized by single-crystal X-ray diffraction. Complex 1 reveals a 0-D structure and further forms a 1-D supramolecular structure by intermolecular π–π interactions. Complex 2 also displays a 0-D structure, but it extends to 2-D supramolecular networks through weak Cu⋯S interactions. However, complex 3 features a 1-D wavy chain structure bearing weak Cu⋯Cl interactions to form 2-D networks. Complex 4 exhibits a 2-D netlike structure. The experimental results display that the coordination modes of the ligand bmt are corresponded with the computed results. Furthermore, the fluorescence emissions of complexes 3 and 4 in a solid state at room temperature may be assigned to ligand-to-metal charge-transfer (LMCT).[Cu(bmt)4] · (Cl)2 · 4H2O (0-D), [Cu(bmt)2(NCS)2] (0-D), [Cu(bmt)Cl]n (1-D) and [Ag(bmt)(NO3)]n (2-D) have been synthesized and characterized by single-crystal X-ray diffraction and fluorescence spectra.
Co-reporter:Jinpeng Li, Linke Li, Hongwei Hou, Yaoting Fan, Lihong Gao
Inorganica Chimica Acta 2009 Volume 362(Issue 13) pp:4671-4677
Publication Date(Web):15 October 2009
DOI:10.1016/j.ica.2009.06.035
Using sodium 2-chloro-4-ferrocenylbenzoate as functional ligand, a mononuclear precursor complex [Cd(η2-OOCClH3C6Fc)2(H2O)3](CH3OH)2} P1 [Fc = (η5-C5H5)Fe(η5-C5H4)] was synthesized, which containing facile leaving groups. The substitution reactions of the precursor ferrocenyl carboxylate complex with basic N-containing ligands gave three 1-D polymers [Cd2(μ2-OOCClH3C6Fc)4(bix)]n1 [bix = 1,4-bis(imidazol-1-ylmethyl)benzene)], {[Cd2(η2-OOCClH3C6Fc)3(η-OOCClH3C6Fc)(mbbbm)2](CH3OH)2}n2 [mbbbm = 1,3-bis(benzimidazole-1-ylmethyl)benzene] and [Cd(η2-OOCClH3C6Fc)2(pbbbm)]n3 [pbbbm = 1,4-bis(benzimidazole-1-ylmethyl)benzene]. Single-crystal X-ray analysis reveals that the 1-D chain structures of polymers 1–3 are bridged by bix, mpbbbm and pbbbm, respectively, and the three polymers present some differences in their structures. Our results also show that the structural integrity of the precursor complex can be maintained in the resultant polymers. Electrochemical studies of the four complexes in THF/CH3OH solution indicate that the half-wave potentials of the ferrocenyl moieties in these complexes are all shifted to positive potential compared with that of free 2-chloro-4-ferrocenylbenzoic acid.The substitution reactions of the mononuclear precursor complex P1 with basic N-containing ligands result in three 1-D polymers. These polymers display different 1-D chain structures. The structural integrity of the precursor complex can be maintained in the resultant polymers. Their electrochemistry properties are also investigated.
Co-reporter:Wan Zhou, Xiangru Meng, Yanan Ding, Weiqiang Li, Hongwei Hou, Yinglin Song, Yaoting Fan
Journal of Molecular Structure 2009 Volume 937(1–3) pp:100-106
Publication Date(Web):26 November 2009
DOI:10.1016/j.molstruc.2009.08.022
Two new complexes {[Co(bbbm)1.5(NO3)2]·H2O}n (1) and [Cd(bbbm)1.5(NO3)2]n (2) (bbbm = 1,1’-(1,4-butanediyl)bis-1H-benzimidazole) have been synthesized and structurally characterized. Both complexes are built up by two-dimensional coordination networks with (6, 3) nets. The third-order nonlinear optical (NLO) properties of the two complexes are determined and the results show that they not only possess large third-order NLO absorptive effects, but also display strong refractive behaviors. The hyperpolarizability |γ| values are 2.2 × 10−29 esu for complex 1, and 1.6 × 10−30 esu for complex 2. The NLO effective of complex 1 is stronger than that of 2 due to the decreased π back-donation capacity from Co(II) to Cd(II). Thermal analysis studies show that complex 1 is less stable and begins to decompose at 131 °C. While complex 2 is stable up to 257 °C.
Co-reporter:Yajuan Mu, Yaofei Zhao, Hong Xu, Hongwei Hou, Yaoting Fan
Journal of Molecular Structure 2009 Volume 935(1–3) pp:144-150
Publication Date(Web):29 October 2009
DOI:10.1016/j.molstruc.2009.07.027
Three coordination complexes, namely, {[Hg(bppdca)Cl2]·DMF}n (1), Hg2(bppdca)2Br4 (2) and {[Hg(bppdca)I2]·MeOH}n (3) were synthesized by reactions of HgX2 (X = Cl, Br and I) with ligand N,N′-bis(pyridine-3-yl)pyridine-3,5-dicarboxamide (bppdca). The structures of the complexes were determined by single-crystal X-ray diffraction analyses, and the results reveal that 1 exhibits a two-dimensional (2D) network structure. While 2 is a M2L2 dinuclear metallamacrocycle in which two mercury(II) cations are bridged by two bppdca ligands. In complex 3, bppdca acts as a bidentate ligand to link two mercury(II) atoms to form a one-dimensional (1D) zigzag chain structure. The significant differences in these complexes indicate that anions have a great influence on the formation and structures of complexes. Furthermore, the solid-state fluorescent analyses reveal that complexes 1 and 2 exhibit a broad emission band at 449 and 441 nm, respectively, while complex 3 shows weak emission centered at 438 nm at room temperature.
Co-reporter:Xia Wang, Weiyin Wang, Shumin Liu, Hongwei Hou, Yaoting Fan
Journal of Molecular Structure 2009 938(1–3) pp: 185-191
Publication Date(Web):
DOI:10.1016/j.molstruc.2009.09.024
Co-reporter:Haiyan Yang;Linke Li Dr.;Jie Wu Dr.;Hongwei Hou ;Bo Xiao Dr. ;Yaoting Fan
Chemistry - A European Journal 2009 Volume 15( Issue 16) pp:4049-4056
Publication Date(Web):
DOI:10.1002/chem.200802515
Co-reporter:Xia Wang, Yaru Liu, Hongwei Hou, Jie Wu, Yaoting Fan
Journal of Organometallic Chemistry 2009 694(1) pp: 77-85
Publication Date(Web):
DOI:10.1016/j.jorganchem.2008.10.008
Co-reporter:Yaru Liu, Jinpeng Li, Hongwei Hou, Yaoting Fan
Journal of Organometallic Chemistry 2009 694(18) pp: 2875-2882
Publication Date(Web):
DOI:10.1016/j.jorganchem.2009.03.045
Co-reporter:Jinpeng Li, Linke Li, Hongwei Hou, Yaoting Fan
Journal of Organometallic Chemistry 2009 694(9–10) pp: 1359-1368
Publication Date(Web):
DOI:10.1016/j.jorganchem.2008.12.025
Co-reporter:Yaru Liu, Hongwei Hou, Qianru Chen and Yaoting Fan
Crystal Growth & Design 2008 Volume 8(Issue 4) pp:1435-1442
Publication Date(Web):March 15, 2008
DOI:10.1021/cg701221f
A distinctive multifunctional precursor complex Zn(bafca)2(phen)(H2O), 1 (bafca− = α-benzamido-β-ferrocenylacrylic carboxylate; phen = 1,10-phenantholine), is synthesized. As an acceptor, it takes part in the oligimerization to produce a novel decanuclear Zn(II) cluster, [Zn(OCH3)(HOCH3)(bafca)]10·8H2O, 1A; as a donor, it undergoes the unusual central metal ion exchange reaction, resulting in a new Cd(II) skeleton, [Cd(bafca)2(phen)]2·8H2O, 1B. X-ray crystallographic analysis shows that the molecule of 1A consists of a centrosymmetric ring comprised of 10 Zn(II) ions held together by 10 μ2-methoxide, 10 μ2-methanol, 10 1,3-bridging bafca− ligands. In the ring, the 10 zinc atoms are approximately coplanar and are coordinated in a distorted octahedral manner by six oxygen donor atoms. Compound 1A is the analogue of Lippard’s famous “ferric wheel” [Fe(OMe)2(O2CCH2Cl)]10 of bivalent metal ions ( J. Am. Chem. Soc.1990, 112, 9629; 1994, 116, 823), and its synthesis proves that the bivalent metal ions can also form such wheel structures. Compound 1B has a dinuclear structure with the Cd ions, which are linked by two tridentate bafca−. In addition, we verify that the oligimerization of metal−carboxylate complexes with methanol under basic conditions is a relatively reliable synthetic route to produce wheel structures by the synthesis of a similar planar decanuclear Cd(II) wheel of formula [Cd(OCH3)(HOCH3)(bafca)]10·8H2O·6CH3OH, 2A, which is obtained from the precursor [Cd(bafca)2(H2O)2]2, 2 or 1B, under the same reaction conditions as those used for the preparation of 1A. The strong electrochemical responses of precursors 1 and 2 to 1,1′-(1,4-butanediyl)bis-1H-benzotriazole (bbbt) verify further that N-containing ligands play an important role in the formation of 1A or 2A.
Co-reporter:Huaixia Yang, Xiangru Meng, Yun Liu, Hongwei Hou, Yaoting Fan, Xiaoqing Shen
Journal of Solid State Chemistry 2008 Volume 181(Issue 9) pp:2178-2184
Publication Date(Web):September 2008
DOI:10.1016/j.jssc.2008.04.045
The combination of framework-builders 1,1′-(1,3-propanediyl)bis-1H-benzimidazole (pbbm), Cd(II) ion and framework-regulator ClO4− or SO42− provides two new coordination polymers [Cd(pbbm)2(ClO4)2]n(1) and {[Cd(pbbm)SO4(H2O)2]·CH3OH}n(2). Both of them display 1-D chain framework, but their detailed structures are clearly different from each other. 1 displays a 1-D ribbon of rings framework, 2 features an interesting infinite 1-D looped chain structure composed of two kinds of rings, the smaller 8-membered ring and the larger 20-membered ring. The antimicrobial activities of the two polymers were tested by the agar diffusion method and the results indicated that they exhibited antimicrobial activities against bacterial strands. The measurement of the non-isothermal kinetics of the thermal decomposition of 2 reveals that there are at least three steps that occur in its decomposition process.Two new Cd(II)-containing complexes have been synthesized and characterized by single-crystal X-ray diffraction. The antimicrobial activity and the non-isothermal kinetics of the thermal decomposition of the polymers were also investigated.
Co-reporter:Hong Xu, Zhenyu Chao, Yali Sang, Hongwei Hou, Yaoting Fan
Inorganic Chemistry Communications 2008 Volume 11(Issue 12) pp:1436-1440
Publication Date(Web):December 2008
DOI:10.1016/j.inoche.2008.08.019
Through varying the volume ratio of mixed solvent, we obtained two distinct polymers {[Pb6(2,6-pda)6] · H2O}n (1) (2,6-pda = 2,6-pyridyldicarboxylate) and [Pb(mpcp)(OAc)]n (2) (mpcp = methyl-6-(pyridin-2-ylcarbamoyl)picolinate) by reaction of Pb(OAc)2 · 3H2O and 2,6-dicarboxamido-(2-pyridyl)-pyridine (H2dcapp) decomposed through lead-induced hydrolysis. Photoluminescence investigations reveal that both polymers display enhanced emissions in contrast to the free ligand, respectively.By varying the ratio of DMF/MeOH solvent, we obtained a 3D microporous-structural polymer {[Pb6(2,6-pda)6] · H2O}n (1) (2,6-pda = 2,6-pyridyldicarboxylate) and a 1D chain polymer [Pb(mpcp)(OAc)]n (2) (mpcp = methyl-6-(pyridin-2-ylcarbamoyl)picolinate) via the reaction of Pb(OAc)2 · 3H2O and 2,6-dicarboxamido-(2-pyridyl)-pyridine (H2dcapp), which decomposes through lead-induced hydrolysis.
Co-reporter:Jiyong Hu, Jin’an Zhao, Hongwei Hou, Yaoting Fan
Inorganic Chemistry Communications 2008 Volume 11(Issue 10) pp:1110-1112
Publication Date(Web):October 2008
DOI:10.1016/j.inoche.2008.06.013
Two new cadmium diphosphonate complexes, namely, Cd2(H2O)2[(C5H5N)CH2C(OH)(PO3)(PO3H)]21 and Cd2(H2O)(Cl)[(C5H5N)CH2C(OH)(PO3)2] 2, based on [1-hydroxy-2-(3-pyridyl)-ethylidene]-bis-[phosphonic acid] monosodium salt have been synthesized under hydrothermal reaction and characterized by single crystal X-ray diffraction. Both complexes show strong fluorescence emission in contrast to the free ligand, respectively, in solid state at ambient temperature.Two new cadmium diphosphonate complexes, namely, Cd2(H2O)2[(C5H5N)CH2C(OH)(PO3)(PO3H)]21 and Cd2(H2O)(Cl)[(C5H5N)CH2C(OH)(PO3)2] 2, based on [1-hydroxy-2-(3-pyridyl)-ethylidene]-bis-[phosphonic acid] monosodium salt have been synthesized under hydrothermal reaction. The two complexes both show strong fluorescence emission in contrast to the free ligand, respectively, in solid state at ambient temperature.
Co-reporter:Xiangru Meng, Jinpeng Li, Hongwei Hou, Yinglin Song, Yaoting Fan, Yu Zhu
Journal of Molecular Structure 2008 Volume 891(1–3) pp:305-311
Publication Date(Web):26 November 2008
DOI:10.1016/j.molstruc.2008.03.058
Reactions of 1,1′-(1,3-propylene)bis-1H-benzotriazole (pbbt) and KSCN with Ni(II) or Co(II) salt lead to the formation of two new double helix chain coordination polymers {[Ni(pbbt)2(NCS)2]·H2O}n1 and {[Co(pbbt)2(NCS)2]·H2O}n2. Their third-order nonlinear optical (NLO) properties were determined with a 7 ns pulsed laser at 532 nm. The results show that polymer 2 exhibits large NLO absorptive effects (α2 = 1.4 × 10−9 m W−1), and both of them show strong NLO refractive behaviors with the refractive index n2 of 3.02 × 10−18 m2 W−1 for 1 and 8.23 × 10−18 m2 W−1 for 2. The hyperpolarizability |γ| values of 1 and 2 were calculated to be 1.68 × 10−29 esu and 4.58 × 10−29 esu, respectively. This indicates that the third-order NLO properties of coordination polymers can be altered through metal ions manipulation.
Co-reporter:Bo Xiao, Hongwei Hou, Yaoting Fan
Journal of Molecular Catalysis A: Chemical 2008 Volume 288(1–2) pp:42-51
Publication Date(Web):3 June 2008
DOI:10.1016/j.molcata.2008.02.025
Two new Cu(II)-organic polymers supported by different N-heterocyclic ligands, namely {[Cu(btx)2]·Cl2}n1 (btx = 1,4-bis(triazol-1-ylmethyl)-benzene) and {[Cu(bbbm)(Ac)2]·(CH3OH)2}n2 (bbbm = 1,1′-(1,4-butanediyl)bis-1H-benzimidazole) are designed and synthesized in order to ascertain the influence of coordination polymeric structure on catalytic activity. Single-crystal X-ray diffraction shows that 1 assumes a 2D cationic rhombohedral grid network arrangement, whereas 2 features a 1D zigzag chain structural motif in which Cu atoms are bridged by μ2-bbbm ligands. Both of them reveal impressive catalytic capability for the selectively oxidative coupling of 2,6-di-t-butylphenol to the corresponding diphenoquinone in excellent yield using H2O2 as oxidant and KOH as co-catalyst in water and allow reuse without a significant loss of activity through three runs with the hindered phenol. Under the similar reaction conditions, the two polymers also accelerate the selectively coupling of 2,4-di-t-butylphenol to generate the relevant biphenol with moderate to high efficiencies. The transformation of 2,6-dimethylphenol mediated by polymers 1 and 2 proceeds smoothly with 100% and 94.5% conversion, respectively. It is found that polymer 1 offers the superior results in terms of reactivity and selectivity to 2 for such processes, indicating the crucial role of structural parameters in catalytic performance of polymers. Furthermore, the ability of 1 and 2 to undergo homogeneous oxidation couplings of these substituted phenols in 1.5:1 (v/v) methanol–toluene mixture is explored as well to demonstrate the advantages of heterogeneous catalysis.Two new Cu(II)-organic polymers containing coordinatively unsaturated metal sites are designed and synthesized as competent heterogeneous catalysts for the oxidative coupling of various substituted phenols in aqueous medium. It is suggested that the combination of the physical and chemical properties of inorganic and organic components can allow the achievement of the targeted polymeric materials furnishing unusual catalytic characters.
Co-reporter:Liwei Mi;Hongwei Hou ;Zhiyong Song;Huayun Han Dr. ;Yaoting Fan
Chemistry - A European Journal 2008 Volume 14( Issue 6) pp:1814-1821
Publication Date(Web):
DOI:10.1002/chem.200700782
Abstract
A porous bilayered open coordination polymer [Zn(4,4′-bpy)2(FcphSO3)2]n (1; FcphSO3Na=m-ferrocenyl benzenesulfonate), has been assembled from Zn(NO3)2, m-ferrocenyl benzenesulfonate, and the bridging ligand 4,4′-bipyridine (4,4′-bpy). Ion-exchange induced products [Cd0.6Zn0.4(4,4′-bpy)2(FcphSO3)2]n (2), [Zn0.75Pb0.25(4,4′-bpy)2(FcphSO3)2]n (3), and [Cu0.5Zn0.5(4,4′-bpy)2(FcphSO3)2]n (4) could be obtained directly by suspending a big single crystal of 1 into concentrated solutions of Cd(NO3)2, Pb(NO3)2, and Cu(NO3)2, respectively. Most importantly, the big single crystal of 1 could be partly regenerated after immersion into concentrated aqueous solutions of Zn(NO3)2. On the other hand, powdered 1 could also be used as a metal ion adsorbent because of the well-defined pore size and pore shape. Ion exchange takes place along with the process of ion sorption. The big single crystal of 1 removes harmful metal ions by means of ion exchange, whereas powdered 1 removes toxic metal ions mainly through ion sorption. Also, compound 1 could be employed as a multi-ion analysis fluorescent probe to detect dangerous metal ions, such as Pb2+, Cd2+, Ag+, and Cu2+. The compounds described in this study may have potential applications in the design of new molecular devices.
Co-reporter:Liwei Mi, Hongwei Hou, Zhiyong Song, Huayun Han, Hong Xu, Yaoting Fan and Seik-Weng Ng
Crystal Growth & Design 2007 Volume 7(Issue 12) pp:2553
Publication Date(Web):November 15, 2007
DOI:10.1021/cg070468e
Porous pillared bilayer open coordination polymer {[Cd(bpp)2(O3SFcSO3)]·(CH3OH)2 ·(H2O)6}n 1 (Fc = ferrocene) and 3D porous coordination polymer {[Cd(bpy)2(O3SFcSO3)]·(CH3OH)4}n 2 have been assembled from Cd(NO3)2, ferrocene-1,1′-disulfonate, and bridging ligands 1,3-bis(4-pyridyl)propane (bpp) or 4,4′-bipyridine (bpy). Both of them show very special adsorption properties to copper salts. Along with the increase in the solution concentration of Cu(NO3)2, the percentage of adsorbed copper ions falls, but the percentage of exchanged central cadmium ions and the amount of adsorbed copper ions rises. In dilute solution, there mainly exists metal ion sorption, whereas both ion sorption and exchange are in charge of the whole progress in strong solution. Meanwhile, such materials could be used as ideal metal ion adsorbent toward some other metal cations, including of Pb2+, Zn2+, Mn2+, Co2+, Ni2+. However, when all these metal ions coexist in a mixture solution, the two ferrocenyl complexes selectively adsorb large amounts of only Pb2+ (for 1, 88.54%; for 2, 75.80%) and Cu2+ (for 1, 90.94%; for 2, 79.45%). Ion sorption and central cadmium ion exchange might be considered as being dominated by the coordination ability of metal ions to free functional groups, ionic radii of adsorbed metal ions, and the solution concentration of adsorbed metal salts. On the basis of the recognition of ion exchange, the center metal ion-exchange product of 2, {[Cd0.5Cu0.5(bpy)2(O3SFcSO3)]·(CH3OH)4}n 3, could be obtained by ion-exchange-induced single crystal to single crystal transformation.
Co-reporter:Liwei Mi;Hongwei Hou;Jiaqiang Xu;Hong Xu;Zhiyong Song;Mingsheng Tang;Yaoting Fan
European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 33) pp:
Publication Date(Web):2 OCT 2007
DOI:10.1002/ejic.200700407
The inclusion complex [{Co(bpy)(H2O)4}·(fcds)]n (1), which has been constructed using the guest molecule ferrocene-1,1′-disulfonate (fcds), the bridging ligand 4,4′-bipyridine (bpy) and d7 Co2+, contains an infinite zigzag chain formed by the central CoII ion and the bridging bpy ligand. Guest fcds molecules lie between two adjacent zigzag chains. The highly conjugated structure of complex 1 means that it can be used as a metal-organic semiconductor, and it also shows a high response to liquefied petroleum gas (LPG) and ethanol/petroleum ether (EP) at room temperature. The inclusion complexes [{Co(bpp)2(H2O)2}·(fcds)·4H2O]n [2; bpp = 1,3-bis(4-pyridyl)propane] and [{Zn(bpy)(H2O)4}·(fcds)]n (3), on the other hand, cannot be employed as room-temperature gas sensors because they are insulators. The electrical resistivity of inclusion complex [{Ni(bpy)(H2O)4}·(fcds)]n (4) is 621 MΩ, whereas that of [{Co(bpy)(H2O)4}SO4·(4-abaH)2·3H2O]n (5) (4-abaH = 4-aminobenzoic acid) is only 137 MΩ. This means that the semi-conducting properties of such inclusion complexes depend on both the conjugated structure and the central metal ions. Furthermore, conjugated inclusion complexes with an odd number of electrons could be useful for the design of highly selective room-temperature gas sensors.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Co-reporter:Xia Wang;Linke Li;Hongwei Hou;Jie Wu;Yaoting Fan
European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 33) pp:
Publication Date(Web):26 SEP 2007
DOI:10.1002/ejic.200700542
With the use of sodium β-ferrocenylacrylate and sodium p-ferrocenylbenzoate as functional ligands, we synthesized mononuclear precursor complexes containing facile leaving groups or coordinatively unsaturated metal ions: [Cd(η2-OOCCH=CHFc)2(C2H5OH)2] (1), {[Cd(η2-OOCC6H4Fc)2(dmf)2(H2O)]} (2), {[Cd(η2-OOCC6H4Fc)2 (phen)(H2O)](CH3OH)} (3), and {[Zn(OOCC6H4Fc)2(phen)](H2O)} (4) (phen = 1,10-phenanthroline). Investigation of the fourprecursor ferrocenyl carboxylate complexes as building blocks resulted in ten complexes. The complexes{[Cd(η2-OOCCH=CHFc)2(bbbm)](H2O)}n (1a), {[Cd2(η2-OOCCH=CHFc)4 (pbbm)2](CH3OH)6(H2O)4} (1b), {[Cd(η2-OOCC6H4Fc)2(py)3] (CH3OH)4} (2a), {[Cd2(η2-OOCC6H4Fc)4(btx)2](thf)3(CH3OH)2} (2b), {[Cd2(η2-OOCC6H4Fc)2(OOCC6H4Fc)2(phen)2(bbbm)] (CH3OH)4(thf)2} (3a), and [Zn(OOCC6H4Fc)2(phen)(H2O)] (4a) were obtained by the substitution or addition reactions of the precursor complexes under moderate conditions. As anticipated, the structural integrity of the precursor complexes can be maintained from the precursors to these complexes. We designed the structures of the complexes by controlling the number of leaving groups in the precursor complexes. In addition, a recombination may have taken place in the reactions of the precursor complexes with organic ligands under severe conditions. The “recombinant” complexes {[Cd2(η2-OOCCH=CHFc)2(μ2-η2-OOCCH=CHFc)2(L)2](CH3OH)4}n [L = 1,4-bis(imidazol-1-ylmethyl)benzene (bix), 1c; L = btx, 1d], {[Cd(η2-OOCC6H4Fc)2(pbbm)(H2O)](H2O)}n (3b) and {[Zn(OOCC6H4Fc)2(bbbm)](CH3OH)3}n (4b) were also obtained under reflux conditions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Co-reporter:Jin'an Zhao, Liwei Mi, Hongwei Hou, Xianju Shi, Yaoting Fan
Materials Letters 2007 Volume 61(19–20) pp:4196-4198
Publication Date(Web):August 2007
DOI:10.1016/j.matlet.2007.01.053
Zinc ferrite nanorods were prepared by the decomposition of ferrocenyl complex [Zn(fca)2] 1 (Hfca, ferroceneylacetone) as single source precursor. In this work, we presented a new and simple route to synthesize nanostructured ferrites by decomposition of ferrocene-based complexes without the assistance of catalysts or template, and successfully obtained zinc ferrite nanorods with perfect morphology. The synthesis of ZnFe2O4 nanorods was carried out via decomposition of zinc ferrocenyl complexes at the presence of sodium hypochlorite under hydrothermal condition without the attendance of catalysts or templates. The results show that ferrocenyl complexes play an important role in the control synthesis of good morphology ferrites. To our knowledge, this is the first report to describe the synthesis of nanostructured zinc ferrites based on one-step hydrothermal decomposition of zinc ferrocenyl complexes. This exploration provides a useful method to seek new nanomaterials with perfect morphology in the shape-controlled synthesis of complicated inorganic composition oxides.
Co-reporter:Xiaoli Zhou, Xiangru Meng, Wei Cheng, Hongwei Hou, Mingsheng Tang, Yaoting Fan
Inorganica Chimica Acta 2007 Volume 360(Issue 11) pp:3467-3474
Publication Date(Web):1 August 2007
DOI:10.1016/j.ica.2007.03.008
Two Cu(II)-containing complexes, [Cu(pbbt)Cl2]2 · CH3OH (1) and [Cu(bbbt)1.5Cl2]n (2) (pbbt = 1,1′-(1,3-propylene)bis-1H-benzotriazole, bbbt = 1,1′-(1,4-butanediyl)bis-1H-benzotriazole), have been synthesized and characterized. Single crystal X-ray diffraction shows that 1 exhibits discrete binuclear structure, in which two Cu(II) ions are bridged together through two Cl− anions and two pbbt ligands. Whereas 2 displays infinitely extended two-dimensional reticulate grid structure with hexagon units in which six Cu(II) ions act as corners and six bbbt ligands serve as sides. The electrochemical studies show that their redox processes in the potential range of 0.1–0.9 V are quasi-reversible and controlled by diffusion. The diffusion coefficients decrease with increase in the molecular weight of the complexes and the size of the molecules. Further investigation exhibits that their electrochemical properties obtained from experiments are consistent with their crystal data and the computed parameters. For example, the observed one-pair well-defined redox waves in the cyclic voltammetry (CV) diagrams correspond to the X-ray diffraction results that all of the Cu(II) ions in the title complexes are equivalent, respectively; the cathodic shifts (as compared with CuCl2) of the reduction potentials of 1 and 2 are in agreement with the computed results: the LUMO energies of the complexes (−3.789 eV for 1 and −4.330 eV for 2) are higher than that of CuCl2 (−6.942 eV).Two Cu(II)-containing complexes have been synthesized and systematically characterized by single crystal X-ray diffraction, CV, CA, CC, spectroscopic and B3LYP/genecp methods and so on. Further investigation exhibits that their electrochemical properties obtained from experiments are consistent with their crystal data and the computed results.
Co-reporter:Yunyin Niu, Ning Zhang, Hongwei Hou, Yu Zhu, Mingsheng Tang, SeikWeng Ng
Journal of Molecular Structure 2007 Volume 827(1–3) pp:195-200
Publication Date(Web):17 February 2007
DOI:10.1016/j.molstruc.2006.05.029
Solution reaction of Cu(I) iodide with organic multifunctional ligands generated two different structure motifs: 0D cluster [(CuI)2(dpds)2] 1 (dpds = 2,2′-dipyridyldisulfide), and 1D polymer [(CuI)(bbbm)]n2 (bbbm = 1,1′-(1,4-butanediyl)bis-1H-benzimidazole). Both compounds contain the flexible rhomboid Cu2I2 cluster unit. The solution-state luminescence spectra showed that the high-energy emission may be associated with a metal-to-ligand [Cu → π∗(pyridine)] or ligand-to-ligand [I− → π∗(pyridine)] charge-transfer excited state.
Co-reporter:Hong Xu, Yinglin Song, Liwei Mi, Hongwei Hou, Mingsheng Tang, Yali Sang, Yaoting Fan and Yan Pan
Dalton Transactions 2006 (Issue 6) pp:838-845
Publication Date(Web):02 Nov 2005
DOI:10.1039/B508177G
Three metal–organic polymers, [CoCl2(bpfp)]n1, {[NiCl2(bpfp)2](H2O)3}n2 and [ZnCl2(bpfp)]n3
(bpfp =
N,N′-bis(3-pyridylformyl)piperazine), are formed by the self-assembly of the flexible bpfp with MCl2
(M = Co, Ni, Zn), respectively. X-Ray single-crystal structural analysis reveals that polymer 1 exhibits a novel grid network, in which the grid is composed of segments of bpfp and cobalt ions. Polymer 2 consists of 2D rhombohedral grids, the dimensions of the grid are 15.782 × 12.434 Å2 and the diagonal-to-diagonal distances are 13.186 × 25.169 Å2. In polymer 3, infinite wavelike chains are extended to 2D supramolecular arrays via C–H⋯Cl hydrogen bonds. The third-order nonlinear optical (NLO) behaviors of 1–3 and bpfp were investigated in dilute DMF solution by Z-scan measurement. The results show that 1, 2 and 3 exhibit good third-order NLO properties, which are quite different from bpfp that shows weak NLO behavior. This paper demonstrates that metal ions can strongly influence the crystal structures and third-order NLO properties of polymers.
Co-reporter:Huayun Han, Yinglin Song, Hongwei Hou, Yaoting Fan and Yu Zhu
Dalton Transactions 2006 (Issue 16) pp:1972-1980
Publication Date(Web):18 Jan 2006
DOI:10.1039/B514431K
In this paper four metal–organic polymers {[Zn(fcz)Cl2]·CH3OH}n1, {[Cd(fcz)2Cl2]·CH3OH·2H2O}n2, {[Co(fcz)2Cl2]·2CH3OH}n3 and {[Cu(fcz)2Cl2]·2CH3OH}n4 (fcz = fluconazole: α-(2,4-difluorophenyl)-α-(1H-1,2,4-triazol-l-ylmethyl)-1H-1,2,4-triazole-l-ethanol) were synthesized and characterized by X-ray single crystal diffraction. Polymer 1 consists of 1-D infinite chains arranged along the b-axis. All of polymers 2–4 exhibit a 2-D rhombohedral grid structure. We study the third-order nonlinear optical properties of fcz and polymers 1–4 in DMF solution by using 8 ns laser pulses at 532 nm, and find that 1 and 4 exhibit different NLO properties from fcz and both 2 and 3 show similar NLO properties to fcz. 1 possesses strong NLO refractive effects and large NLO absorptive behaviors. 2, 3 and fcz exhibit strong refractive effects, but their NLO absorptive behaviors are weaker than that of 1. The NLO effects of 4 are very weak. The study of optical limiting (OL) effects by using 40 ps laser pulses at 532 nm shows that fcz and polymer 3 possess a strong OL effect. The optical limiting threshold values of 0.15 J cm−2 for fcz and 0.16 J cm−2 for 3 are comparable to those of many heterothiometallate clusters. Polymers 1, 2 and 4 show a weak OL effect. The fluorescent spectra in DMF solution (concentration: 1 × 10−4 mol dm−3) show that polymers 1–4 exhibit different luminescence properties from fcz. The maximum wavelength of polymers 1–3 are blue shifted gradually by 2–12 nm while polymer 4 exhibits a fluorescent self-quenching phenomenon. These results demonstrate that metal ions play an important part in the NLO and fluorescent properties of coordination polymers.
Co-reporter:Yunyin Niu;Yinglin Song;Ning Zhang;Hongwei Hou;Deji Che;Yaoting Fan;Yu Zhu;Chunying Duan
European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 11) pp:
Publication Date(Web):31 MAR 2006
DOI:10.1002/ejic.200500950
The solution-phase reactions of metal iodides or iodine with 1,3-bis(4-pyridyl)propane (bpp) yields four new organic–inorganic hybrid frameworks, namely [(CuI)4(bpp)4]n(1), [(AgI)6(bpp)]n (2), [PbI2(bpp)]n (3), and [I3(bppH)] (4), each of which adopts a different structural motif. For example, complex 1 is a 2D “open” coordination polymeric cluster consisting of a CuI2Cu rhomboid cluster core coordinated by anti-anti and anti-gauche bpp interactions to produce an interpenetrating 2D (4,4) polycatenane net; 2 is a novel bpp inclusion compound with a unique 2D polymeric hexagonal prism-shaped [Ag6I6]n cluster motif; compound 3 is also a 2D “open” supramolecular cluster made from [PbI2]n “ribbons” and bpp bridges; compound 4 is a triiodide made up of organic [bppH]+ cations and a I3– anion chain. The clusters 1–3 obtained from the reaction between polyiodide complexes and an organic ligand suggest that this simple synthetic approach is likely to be applicable to the construction of polymeric clusters. The third-order NLO effects of 1 were studied by Z-scan techniques. The polymeric cluster exhibits good nonlinearities and the effective third-order NLO refractive index (n2) value is 2.56 × 10–12 esu which is comparable to those of most cluster monomers and polymers. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Co-reporter:Huayun Han;Sujuan Zhang;Hongwei Hou;Yaoting Fan;Yu Zhu
European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 8) pp:
Publication Date(Web):23 FEB 2006
DOI:10.1002/ejic.200500808
In this paper three coordination polymers, {[Fe(fcz)2Cl2]·2CH3OH}n (1), {[Cu(fcz)2(H2O)]·SO4·DMF·2CH3OH·2H2O}n (2), and {[Cu(fcz)2Cl2]·2CH3OH}n (3) {fcz = 1-(2,4-difluorophenyl)-1,1-bis[(1H-1,2,4-triazol-l-yl)methyl]ethanol}, were synthesized. Crystallographic analysis reveals that polymer 1 exhibits a 2-D rhombohedral grid structure with (4, 4) nets, while polymer 2 has a 1-D double-chain framework. The structure of polymer 3 is similar to that of 1. We found that polymers 1–3 could effectively catalyze the oxidation of benzyl alcohol to benzaldehyde with H2O2 (30 mass-%) as oxidant in aqueous medium. Various reaction conditions were studied, and optimal reaction conditions were obtained. Under the optimal conditions, the selectivity to benzaldehyde was almost up to 100 % and the conversion of benzyl alcohol was 87 % for 1, 79 % for 2, and 68 % for 3. The results of the recycling test showed that the catalytic activity decreased by only about 7 % after three consecutive reaction cycles. However, under similar conditions, when we used the corresponding metal salt instead of the polymer as catalyst, or replaced the water with acetonitrile as solvent, neither the selectivity nor the conversion was the same. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Co-reporter:Linke Li, Jinpeng Li, Hongwei Hou, Yaoting Fan, Yu Zhu
Inorganica Chimica Acta 2006 Volume 359(Issue 10) pp:3139-3146
Publication Date(Web):1 July 2006
DOI:10.1016/j.ica.2006.03.002
One-dimensional lanthanide–ferrocenesuccinate polymeric complexes [M(η2-FcCOC2H4COO)(μ2-η2-FcCOC2H4COO)2(H2O)2]n (Fc = (η5-C5H4)Fe(η5-C5H4), M = Pr, 1; Ce, 2; La, 3) have been synthesized and structurally characterized by single-crystal X-ray crystallography. The three polymers are isomorphous, in which each Ln(III) ion is 10-coordinated and connects with two water molecules and eight oxygen atoms from ferrocenesuccinate units in two kinds of coordination modes: bidentate-chelating mode and tridentate-bridging mode. The variable-temperature magnetic susceptibility in the temperature range 5–300 K for 1 and 2 shows that both of them display weak antiferromagnetic interaction. In addition, the redox and fluorescent properties have been investigated. The redox properties are different from the previous results of transition metal compounds containing ferrocenyl systems. Compared with sodium ferrocenesuccinate, polymers 1 and 3, the fluorescent intensities of 2 are markedly enhanced in the solid state.One-dimensional lanthanide–ferrocenesuccinate isomorphous polymers [M(η2-FcCOC2H4COO)(μ2-η2-FcCOC2H4COO)2(H2O)2]n (Fc = (η5-C5H4)Fe(η5-C5H4), M = Pr, 1; M = Ce, 2; M = La, 3) were synthesized and structurally characterized. Polymers 1 and 2 both display weak antiferromagnetic interaction. The redox properties are different from the previous results of transition metal compounds containing ferrocenyl systems. Compared with sodium ferrocenesuccinate, polymers 1 and 3, the fluorescent intensities of 2 are markedly enhanced in the solid state.
Co-reporter:Linke Li, Haiyan Yang, Yinglin Song, Hongwei Hou, Yaoting Fan
Inorganica Chimica Acta 2006 Volume 359(Issue 7) pp:2135-2140
Publication Date(Web):25 April 2006
DOI:10.1016/j.ica.2006.01.031
Two cobalt(II) coordination polymers {[Co(SCN)2(3-bpit)2] · 2CH3OH}n (1) (3-bpit = N,N′-bis(3-pyridylformyl)imidazolidine-2-thione) and {[Co(SCN)2(4-bpit)2] · CH3OH · CH3CN}n (2) (4-bpit = N,N′-bis(4-pyridylformyl)imidazolidine-2-thione) have been synthesized for study of the third-order non-linear properties. X-ray crystal structural analyses reveal that the two polymers show the same topological motif: a ribbon of rings. Their third-order non-linear optical (NLO) properties in DMF solution have been studied by Z-scan techniques with a linearly polarized laser light (λ = 532 nm; pulse widths = 7 ns). Both of them exhibit strong self-focusing effect. The third-order NLO susceptibility χ(3) values are calculated to be 2.61 × 10−11 esu (1) and 2.76 × 10−11 esu (2), respectively. The values are comparable to those of the reported good NLO materials.Two cobalt(II) coordination polymers {[Co(SCN)2(3-bpit)2] · 2CH3OH}n (1) (3-bpit = N,N′-bis(3-pyridylformyl)imidazolidine-2-thione) and {[Co(SCN)2(4-bpit)2] · CH3OH · CH3CN}n (2) (4-bpit = N,N′-bis(4-pyridylformyl)imidazolidine-2-thione) have been synthesized for study of the third-order non-linear properties. X-ray crystal structural analyses reveal that the two polymers show the same topological motif: a ribbon of rings. Both of them exhibit strong self-focusing effect. The third-order NLO susceptibility χ(3) values are calculated to be 2.61 × 10−11 esu (1) and 2.76 × 10−11 esu (2), respectively. The values are comparable to those of the reported good NLO materials.
Co-reporter:Jie Wu;Yinglin Song ;Erpeng Zhang;Hongwei Hou ;Yaoting Fan ;Yu Zhu
Chemistry - A European Journal 2006 Volume 12(Issue 22) pp:
Publication Date(Web):24 MAY 2006
DOI:10.1002/chem.200500905
Reaction of FcCH2PO3H2 [Fc=(η5-C5H5)Fe(η5-C5H4)] (H2FMPA) and 1,10-phenanthroline (phen) with Cd(OAc)2⋅2 H2O or ZnSO4⋅7 H2O in methanol in the presence of triethylamine resulted in the formation of two new ferrocenylphosphonate metal-cage complexes [M4(fmpa)4(phen)4]⋅ 7 CH3OH (M=Cd 1, M=Zn 2). Both structures contain two kinds of isomeric tetranuclear metal phosphonate cages, which are linked to one another by π–π interactions between the phen molecules. In 1, the Cd1, Cd3, and Cd4 atoms are all pentacoordinate, while the Cd2 atom is coordinated by four oxygen atoms from three phosphonate ligands and two nitrogen atoms from the chelating phen in a distorted octahedral geometry. Four Cd atoms from each unit are interconnected through bridging phosphonate ligands with different coordination modes, such as 5.221, 4.211, and 2.11 (Harris notation), yielding a {Cd4} cage. In 2, each Zn atom is coordinated by three oxygen atoms from three phosphonate ligands and two nitrogen atoms from phen, leading to a distorted square-pyramidal geometry. The four Zn atoms of each isomeric unit are also interconnected through four bridging phosphonate ligands to yield a {Zn4} cage. Fluorescent studies indicate that ligand-to-ligand charge-transfer photoluminescence is observed for 1, while the emisson bands of 2 can be assigned to an admixture of ligand-to-ligand and metal-to-ligand charge transfer. Solution-state differential pulse voltammetry indicates that the half-wave potentials of the ferrocenyl moieties in 1 and 2 have different deviations relative to the relevant H2FMPA ligand. This may be because the highest occupied molecular orbital (HOMO) in 1 is located in the FMPA2− groups, while in 2 the HOMO is located in the phen and ZnII groups, so the FeII centers in complex 1 are more easily oxidized to FeIII centers than those of 2. The third-order nonlinear optical (NLO) measurements show that both 1 and 2 exhibit strong third-order NLO self-focusing effects; hence, they are promising candidates for NLO materials. By calculating the component of the lowest unoccupied molecular orbitals of 1 and 2, we confirmed that the co-planar phen rings control their optical nonlinearity, while the H2FMPA ligands and metal ions have only a weak influence on their NLO properties.
Co-reporter:Lin Ke Li;Ying Lin Song;Hong Wei Hou;Yao Ting Fan;Yu Zhu
European Journal of Inorganic Chemistry 2005 Volume 2005(Issue 16) pp:
Publication Date(Web):12 JUL 2005
DOI:10.1002/ejic.200500069
The zero-dimensional polymer [Pb6(μ2OOCCH=CHFc)2(μ3-OOCCH=CHFc)2(μ2-η2-OOCCH=CHFc)2(η2-OOCCH=CHFc)2(μ4-O)2] (1), the one-dimensional chain polymers [Pb(η1-μ2-OOCCH=CHFc)2(phen)]n (phen = phenanthroline; (2), {[Cd(μ2-η2-OOCCH=CHFc)(η2-OOCCH=CHFc)(H2O)2](H2O)4}n (3), and the two-dimensional hybrid polymer {[Cd(η2-OOCCH=CHFc)(bbbm)1.5Cl]·1.5H2O}n [bbbm = 1,1'-(1,4-butanediyl)bis-1H-benzimidazole; 4] have been prepared by the reaction of sodium β-ferrocenylacrylate [FcCH=CHCOONa, Fc = (η5-C5H5)Fe(η5-C5H4)] with the appropriate metal salts. Solution-state differential pulse voltammetry for 1–4 indicated that the half-wave potentials of the ferrocenyl moieties in these polymers are all shifted to positive potential compared with that of sodium β-ferrocenylacrylate. The four polymers’ third-order nonlinear optical (NLO) properties were determined by the Z-scan technique in DMF solutions. The results show that these polymers possess good nonlinear optical refraction effects. Their hyperpolarizability (γ) values are calculated to be 4.80 × 10–30, 5.19 × 10–30, 1.57 × 10–29, and 2.04 × 10–29 esu for 1–4, respectively. The γ values of the CdII polymers (3 and 4) are slightly larger than those of the PbII polymers (1 and 2), which indicates that the metal ions play an important role in the NLO properties of these polymers. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Co-reporter:Xiangru Meng, Yaru Liu, Yinglin Song, Hongwei Hou, Yaoting Fan, Yu Zhu
Inorganica Chimica Acta 2005 Volume 358(Issue 11) pp:3024-3032
Publication Date(Web):1 July 2005
DOI:10.1016/j.ica.2005.03.045
Two coordination polymers {[Zn(btx)2(NO3)2]}n (1) and {[Pb(btx)1.5(NCS)]NO3}n (2) (btx = 1,4-bis(triazol-1-ylmethyl)benzene) have been synthesized and characterized by X-ray diffraction. Polymer 1 exhibits a 2-D network with square grid units and polymer 2 possesses an unusual 2-D layered structure with 78-membered rings. By studying the third-order nonlinear optical properties of ligand btx, polymers 1 and 2, we find that they all show strong self-focusing effects. A reasonably good fit between the experimental data and the theoretical curves suggests that the experimentally obtained NLO effects are effectively third-order in nature. The refractive index n2 values are 4.50 × 10−18 m2 W−1 for btx, 3.09 × 10−18 m2 W−1 for 1, and 6.01 × 10−18 m2 W−1 for 2. All these data can match those of the best-known third-order NLO materials such as inorganic oxides, semiconductors, and cluster compounds. In addition, we discuss the influence of the ligand and central metals on the third-order NLO properties of coordination polymers.2-D polymers {[Zn(btx)2(NO3)2]}n (1) and {[Pb(btx)1.5(NCS)]NO3}n (2) (btx = 1,4-bis(triazol-1-ylmethyl)benzene) with large circuits are synthesized and their third-order NLO properties are investigated. We found that the effects of metal ions on the third-order NLO properties of polymers 1 and 2 are weak, and the effects of ligand are crucial.
Co-reporter:Linke Li, Yinglin Song, Hongwei Hou, Zhishan Liu, Yaoting Fan, Yu Zhu
Inorganica Chimica Acta 2005 Volume 358(Issue 11) pp:3259-3266
Publication Date(Web):1 July 2005
DOI:10.1016/j.ica.2005.03.051
Two bis(pyridyl) ligands: N,N′-bis(4-pyridyl)-1,4-benzenedicarboxamide (bpba) and N,N′-bis(3-pyridylformyl)imidazolidine-2-thione (bpit) have been designed and synthesized. Self-assembly of the linear ligand bpba and angular ligand bpit with HgI2 results in a one-dimensional zigzag polymer {[HgI2(bpba)] · 1.5CH3OH}n (1) and a binuclear metallamacrocycle [HgI2(bpit)]2 · 3H2O (2), respectively. Single crystal X-ray diffraction analyses reveal that in the crystal structure of 1 the linear ligand bpba is in transoid conformation, while in the crystal structure of 2 the angular ligand bpit coordinates with HgI2 in cisoid conformation, the different geometries of the two ligands attribute to forming the dissimilar frameworks of two HgI2 adducts. The determination of third-order nonlinear optical (NLO) properties of 1 and 2 in DMF solution shows that adducts 1 and 2 possess strong NLO self-focusing effect. The hyperpolarizability γ values of 1 and 2 are calculated to be 2.10 × 10−29 and 3.24 × 10−29 esu, respectively, which are comparable to those of some NLO materials. And the result indicates that the heavier atoms Hg and I together with the polymeric aggregation play an important role in determining their NLO properties.One-dimensional zigzag polymer {[HgI2(bpba)] · 1.5CH3OH}n (1) and binuclear metallamacrocycle [HgI2(bpit)]2 · 3H2O (2) were prepared based on linear and angular bipyridine ligands, respectively. Third-order nonlinear optical (NLO) properties of 1 and 2in DMF solution show that adducts 1 and 2 possess strong NLO self-focusing effect. The hyperpolarizability γ values of 1 and 2 are 2.10 × 10−29 and 3.24 × 10−29 esu, respectively. And the result shows that the heavier atoms Hg and I together with the polymeric aggregation play an important role in determining their NLO properties.
Co-reporter:Chang Qing;Meng Xiang-Ru;Song Ying-Lin
Chinese Journal of Chemistry 2005 Volume 23(Issue 6) pp:
Publication Date(Web):12 JUL 2005
DOI:10.1002/cjoc.200590725
Treatment of 1,1′-(1,4-butylene)bis-1H-benzimidazole) (bbbi) with CoSO4·7H2O afforded a novel metal-organic polymer [Co(bbbi)1.5(SO4)]n (1), where the central Co(II) ions are bridged by bbbi ligands, leading to a two-dimensional layer with reversed triangular-prism shaped units. Each reversed triangular-prism shaped unit is made up of six bbbi ligands and six cobalt atoms. Thermal analysis revealed that polymer 1 was stable below 147 °C, and oxidized and decomposed to Co2O3 at about 787 °C, and to CoO at about 914 °C.
Co-reporter:Hongwei Hou ;Yongli Wei Dr.;Yinglin Song ;Liwei Mi;Mingsheng Tang ;Linke Li;Yaoting Fan
Angewandte Chemie 2005 Volume 117(Issue 37) pp:
Publication Date(Web):11 AUG 2005
DOI:10.1002/ange.200463004
Der Schweratomeffekt kann den Unterschied in den nichtlinearen optischen Eigenschaften dritter Ordnung der Cluster [Ag10(dcapp)4](OH)2⋅12 H2O (1, siehe Struktur), [Zn4O(dcapp)3]⋅6 H2O (2) und [Hg2(dcapp)2] (3) nicht erklären (H2dcapp=2,6-Dicarboxamido-2-pyridylpyridin). Quantenchemischen Rechnungen zufolge werden die NLO-Eigenschaften von 1 durch das Metall und den Liganden beeinflusst, die von 2 und 3 nur durch den Liganden.
Co-reporter:Hongwei Hou, Yongli Wei, Yinglin Song, Liwei Mi, Mingsheng Tang, Linke Li,Yaoting Fan
Angewandte Chemie International Edition 2005 44(37) pp:6067-6074
Publication Date(Web):
DOI:10.1002/anie.200463004
Co-reporter:Gang Li, Hongwei Hou, Zifeng Li, Xiangru Meng and Yaoting Fan
New Journal of Chemistry 2004 vol. 28(Issue 12) pp:1595-1599
Publication Date(Web):22 Nov 2004
DOI:10.1039/B406983H
Two novel ferrocene-containing Zn(II) coordination polymers, [Zn{μ2-OOCCH(CH3)CFc}2]n [1, Fc=(η5-C5H5)Fe(η5-C5H4)] and {[Zn2{μ2-OOCCH(CH3)CFc}4(bpa)]·2MeOH}n [2, bpa = 1,2-bis(4-pyridyl)ethane], have been prepared. The two polymers have been characterized by single-crystal X-ray crystallography. The Zn(II) ions in polymer 1 are bridged by μ2-coordinated FcC(CH3)CHCOO− anions, forming an infinite [Zn(μ2-OOCH(CH3)CFc}2]n chain. Polymer 2 is constructed from paddle-wheel shaped [Zn2{μ2-OOCCH(CH3)CFc}4] building units. The dimeric tetrabridged cores are connected by organic bridging ligands, leading to a linear [Zn2{μ2-OOCCH(CH3)CFc}4(bpa)]n chain. To the best of our knowledge, 2 is the first example of a Zn(II) polymer built up by ferrocene-based paddle-wheel building units. The electrochemical properties of both polymers were also investigated.
Co-reporter:Hongwei Hou, Lixia Xie, Gang Li, Tiezhu Ge, Yaoting Fan and Yu Zhu
New Journal of Chemistry 2004 vol. 28(Issue 2) pp:191-199
Publication Date(Web):01 Dec 2003
DOI:10.1039/B307384J
Treatment of 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (bpodz) with AgNO3, Cu(OAc)2, CoSO4, CdI2 or MnSO4 afforded five complexes, the coordination polymers [Ag(bpodz)(μ-NO3)]n
(1), {[Cu2(bpodz)(μ-OAc)4](CH3OH)2}n
(2), {[Co(bpodz)(SO4)(H2O)3](CH3OH)2}n
(3) and [Cd(bpodz)2(μ-I)2]n
(4), and the complex [Mn(bpodz)2(SCN)2(H2O)2]
(5). These compounds have been structurally characterized by X-ray single crystal diffraction. 1 is a 2-D network polymer constructed by ladder-like chains. In these chains, the nitrate anions are shared by two silver(I) to form a rhombic Ag2O2 plane. Polymer 2 is a 1-D wave-like chain in which the copper(II) atoms bridged by the acetate groups are separated by a distance of 2.623 Å. Polymer 3 shows a 1-D linear structure, in which interchain H-bonding interactions contribute to the final 2-D networks. Polymer 4 crystallizes as infinite CdI2 chains in which cadmium(II) ions are doubly bridged by pairs of iodine atoms; the bpodz complete the octahedral coordination of the cadmium atoms, but act as monodentate ligands so do not to link the CdI2 chains to form extended 2-D layers. Complex 5 is constructed into a 2-D stair-like structure through hydrogen bonds. Magnetic susceptibility data for polymer 2, measured from 5 to 300 K, show strong antiferromagnetic coupling. These data were fitted to the appropriate equations derived from the Hamiltonian H=−2JS1S2, giving the parameter −2J=320 cm−1.
Co-reporter:Yongli Wei;Hongwei Hou;Yaoting Fan;Yu Zhu
European Journal of Inorganic Chemistry 2004 Volume 2004(Issue 19) pp:
Publication Date(Web):22 JUL 2004
DOI:10.1002/ejic.200400110
The reactions of different transition metals with the multidentate ligand N,N′-bis(1,3,4-thiadiazol-2-yl)-2,6-pyridinedicarboxamide (btapca) afford six new polynuclear complexes: the hexanuclear complexes [{Zn6(O)2(btapca)4}·3DMF·2H2O] (1) and [{Zn6(O)2(btapca)4}·DMF·MeOH·H2O] (2); the pentanuclear complexes [{Zn5(OH)2(btapca)4}·4DMF·H2O] (3), [{Co5(OH)2(btapca)4}·4DMF·MeOH·H2O] (4) and [{Ni5(OH)2(btapca)4}·4DMF·MeOH] (5); and the trinuclear complex [{Fe3(OH)(btapca)3}·2DMF·2MeOH] (6). The dominant characteristic of these polynuclear complexes is that there are μ3- or μ4-oxygen atoms in the metal polyhedrons. The hexanuclear complexes 1 and 2 show similar octahedral features based on zinc centers. The five metal centers in complexes 3, 4 and 5 arrange into two triangles with one common vertex. As for complex 6, three iron(II)/iron(III) atoms form a plane with a μ3-OH− in the center. We also report the magnetic properties of complexes 4, 5 and 6. Complex 4 exhibits intramolecular antiferromagnetic exchange, while the analogous complex 5 is dominated by very strong intramolecular ferromagnetic coupling. The trinuclear complex [{Fe3(OH)(btapca)3}·2DMF·2MeOH] (6) shows comparable weak antiferromagnetic coupling. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Co-reporter:Hong Xu, Yinglin Song, Hongwei Hou
Inorganica Chimica Acta 2004 Volume 357(Issue 12) pp:3541-3548
Publication Date(Web):10 September 2004
DOI:10.1016/j.ica.2004.05.007
Two novel Co(II) coordination polymers {[Co(H2O)2(CH3OH)2(4-bpfp)](NO3)2}n1 (4-bpfp=N,N′-bis(4-pyridylformyl)piperazine) and [Co(NCS)2(CH3OH)2(3-bpfp)]n2 (3-bpfp=N,N′-bis(3-pyridylformyl)piperazine) have been synthesized and characterized by single crystal X-ray diffraction. Both the polymers consist of one-dimensional chains constructed by bridging bpfp ligands and Co(II) ions. The existence of O⋯H–O hydrogen bond in 1 and S⋯H–O hydrogen bond in 2 play important roles in creating interesting supramolecular structures. Their third-order nonlinear optical (NLO) properties in DMF solution have been studied by Z-scan technique. The results reveal that polymers 1 and 2 exhibit strong NLO absorption effects (α2=9.00×10−11 m W−1 for 1; 1.41 × 10−10 m W−1 for 2) and self-focusing performance (n2=3.24×10−16 esu for 1; 3.05 × 10−16 esu for 2) in DMF solutions. The corresponding effective NLO susceptibilities χ(3) values are 3.08 × 10−12 esu (1) and 4.70 × 10−12 esu (2). All of the values are comparable to those of the reported good NLO materials. Additionally, the TG-DTA results of the two polymers are in agreement with the crystal structures.Two novel 1D Co(II) coordination polymers {[Co(H2O)2(CH3OH)2(4-bpfp)](NO3)2}n1 (4-bpfp=N,N′-bis(4-pyridylformyl)piperazine) and [Co(NCS)2(CH3OH)2(3-bpfp)]n2 (3-bpfp=N,N′-bis(3-pyridylformyl)piperazine) have been synthesized and characterized by single crystal X-ray diffraction as well as thermoanalysis. The studies of third-order nonlinear optical (NLO) properties reveal that both the polymers in DMF solutions exhibit strong NLO absorption effects and self-focusing performance, which are comparable to the reported good NLO materials.
Co-reporter:Xiangru Meng, Bo Xiao, Yaoting Fan, Hongwei Hou, Gang Li
Inorganica Chimica Acta 2004 Volume 357(Issue 5) pp:1471-1477
Publication Date(Web):25 March 2004
DOI:10.1016/j.ica.2003.12.009
By the design of ligand 1,1′-(1,5-pentamethylene)bis-1H-benzimidazole (pbbm), we have synthesized polymers {[Co(NO3)(pbbm)2]NO3 · 1/2H2O}n (1), {[CdCl(pbbm)2]Cl · CH3OH}n (2) and {[Cu(Ac)2(pbbm)] · CH3OH}n (3), and characterized their structures by single crystal X-ray diffraction as well as thermoanalysis. In polymers 1 and 2, one of the anions coordinates to the central ion, the other is located in the environment. Two pbbm ligands coordinate simultaneously to two metal centers generating one-dimensional cup-like helical chains. To our best knowledge, this cup-like structure has never been observed in the reported polymers. In polymer 3, each Cu atom is five-coordinate by two nitrogen atoms from two pbbm ligands, and three oxygen atoms from one monodentate acetate anion and one chelating acetate anion leading to one-dimensional wave-like linear chain. In addition, the DTA and TG results of the three polymers are in agreement with the crystal structures.Three coordination polymers {[Co(NO3)(pbbm)2]NO3 · 1/2H2O}n (1), {[CdCl(pbbm)2]Cl · CH3OH}n (2) and {[Cu(Ac)2(pbbm)] · CH3OH}n (3) have been synthesized and characterized by single crystal X-ray diffraction as well as thermoanalysis. Polymers 1 and 2 show one-dimensional cup-like helical chains. To our best knowledge, this cup-like structure has never been observed in the reported polymers. Polymer 3 adopts one-dimensional wave-like linear chain.
Co-reporter:Hongwei Hou, Yongli Wei, Yinglin Song, Yu Zhu, Yaoting Fan
Inorganica Chimica Acta 2004 Volume 357(Issue 2) pp:421-428
Publication Date(Web):30 January 2004
DOI:10.1016/j.ica.2003.05.008
Two novel cluster polymers {[NMe4]2[MoOS3Cu3(μ2-I)3]} 1 and {[NMe4]2[WOS3Cu3(μ2-I)3]}n2 have been prepared. Bithiometalates MO2S22− (M=Mo,W), CuI, Me4NBr and 4,4′-trimethylene-dipyridine(tdp) reacted in solid state under low-heating temperature resulting in these two clusters. X-ray diffraction analysis reveals that the two polymers have the same two-dimensional network structures, which are formed from nest-shaped units along crystallographic b and c directions. I atoms take on a μ2-fashion in bridging all the units. An alternative view along crystallographic a direction shows that they are layered features. Their third-order non-linear optical (NLO) properties were determined by Z-scan techniques. Both compounds possess very strong NLO refractive effect with n2 value of −5.02 × 10−17 m2W−1 for 1 and 1.20 × 10−16 m2W−1 for 2, respectively. Different from routine work, there is an alternation from cluster polymer 1–2 in their optical properties: 1 shows self-defocusing behavior, while 2 gives self-focusing effect. Effective third-order NLO susceptibilities χ(3) were calculated to be 4.90 × 10−11 esu 1 and 1.48 × 10−9 esu 2. The corresponding hyperpolarizabilities γ are 3.39 × 10−28 and 1.02 × 10−26 esu, respectively.Two novel two-dimensional cluster polymers {[NMe4]2[MoOS3 Cu3(μ2-I)3]}n1 and {[NMe4]2[WOS3 Cu3(μ2-I)3]}n2 were described. In the two clusters, I atoms bridge Cu atoms forming Cu–I–Cu–I chains, which make the construction of the extensional 2D networks. They have the same two-dimensional nest-shaped structures, but they show different nonlinear optical (NLO) properties, 1 shows self-defocusing effect, while 2 gives self-focusing effect.
Co-reporter:Yinglin Song, Yunyin Niu, Hongwei Hou, Yu Zhu
Journal of Molecular Structure 2004 Volume 689(1–2) pp:69-74
Publication Date(Web):3 February 2004
DOI:10.1016/j.molstruc.2003.10.025
The structure and molecular packing of a ZnI2-pyrazine adduct are reported. Attractive zigzag I⋯I interactions dominate the molecular packing in the structure and link ZnI2-pyz zigzag chains to result in the formation of three-dimensional network structure. The optical limiting property was studied by Z-scan technology with an 8 ns-pulsed laser at 532 nm. The limiting threshold was determined to be 0.13 J cm−2, which is comparable to those of many heterothiometallates.
Co-reporter:Xiangru Meng, Hongwei Hou, Gang Li, Baoxian Ye, Tiezhu Ge, Yaoting Fan, Yu Zhu, Hiroshi Sakiyama
Journal of Organometallic Chemistry 2004 Volume 689(Issue 7) pp:1218-1229
Publication Date(Web):1 April 2004
DOI:10.1016/j.jorganchem.2004.01.015
Four novel tetranuclear macrocyclic compounds [Cd2(η2-O2CFcCO2)2(2,2′-bpy)2(H2O)2] · 2H2O (1), [Zn2(η2-O2CFcCO2)2(2,2′-bpy)2(H2O)2] · CH3OH · H2O (2), [Co2(O2CFcCO2)2(2,2′-bpy)2(μ2-OH2)2] · CH3OH · 2H2O (3), and [Ni2(O2CFcCO2)2(2,2′-bpy)2(μ2-OH2)2] · CH3OH · 2H2O (Fc=(η5-C5H4)Fe(η5-C5H4) (4) have been synthesized and structurally characterized by single crystal diffraction. The magnetic behaviors for compounds (3) and (4) are studied in the temperature range of 5.0–300 K. The results show that the antiferromagnetic coupling of CoII–CoII pairs occurs in (3), and unusual global ferromagnetic coupling between nickel (II) ions exists in (4). The solution-state differential pulse voltammetries of compounds (1)–(4) all show two peaks with large separations (ΔE) that indicate strong interactions between two ferrocene moieties. Their fluorescent and thermal properties were also investigated.Four novel M–O2CFcCO2-2,2′-bpy (M=Cd, Zn, Co, Ni) tetranuclear macrocyclic compounds have been synthesized and characterized by single crystal diffraction. The magnetic measurements show that an antiferromagnetically coupling of CoII–CoII pairs occurs in compound (3), and unusual global ferromagnetic coupling between nickel (II) ions exists in compound (4). The solution-state differential pulse voltammetries of (1)–(4) all show two peaks with large separations (ΔE) that indicate strong interactions between two ferrocene moieties.
Co-reporter:Hongwei Hou;Gang Li;Yinglin Song;Yaoting Fan;Yu Zhu;Lu Zhu
European Journal of Inorganic Chemistry 2003 Volume 2003(Issue 12) pp:
Publication Date(Web):10 JUN 2003
DOI:10.1002/ejic.200200616
Two novel ferrocenyl complexes [Ag(L)2](NO3)·(MeOH)· (EtOH) (1) and [HgI2(L)] (2) {L = 1,2-bis[(ferrocen-l-ylmethylene)amino]ethane} have been prepared and structurally characterized by means of X-ray single crystal diffraction. The central ion, silver(I) or mercury(II), has a distorted tetrahedral environment, the silver(I) ion coordinates with two L, and the mercury(II) ion binds one L and two iodine atoms. Their third-order nonlinear optical (NLO) properties were determined by Z-scan techniques in DMF solution. The results indicate that the two complexes exhibit very strong NLO absorption and strong self-focusing effects. The third-order NLO absorptive coefficients α2 are 1.34 × 10−8 m W−1 for 1 and 3.1 × 10−9 m W−1 for 2. The refractive indexes n2 for the two complexes are 1.15 × 10−18 and 8.02 × 10−19 m2 W−1, respectively. The hyperpolarizability γ values are calculated to be 2.68 × 10−30 esu for 1 and 1.44 × 10−30 esu for 2. The γ values are several orders of magnitude larger than those of the reported aryl and vinyl derivatives of ferrocene. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
Co-reporter:Yunyin Niu, Yinglin Song, Hongwei Hou, Yu Zhu
Inorganica Chimica Acta 2003 Volume 355() pp:151-156
Publication Date(Web):20 November 2003
DOI:10.1016/S0020-1693(03)00348-7
Two novel coordination polymers incorporating mercury(II) iodide, [Hg (tmp)I2]n (1) (tmp=4,4′-trimethylene dipyridine) and [Hg(azobpy)I2]n (2) (azobpy=3,3′-azobispyridine), have been synthesized via the self-assembly reaction in solution. Their structures were characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 is the first 1D wave-shaped adduct containing HgI2. Complex 2 is a 3D supramolecular framework constructed from HgI2–azobpy zigzag chains linked mutually through Hg⋯I interaction. The optical limiting effects were studied by Z-scan technology with an 8 ns-pulsed laser at 532 nm. Their limiting thresholds were determined to be 0.8 J cm−2 for 1 and 0.4 J cm−2 for 2, which are comparable to those of many heterothiometallates.Reaction of HgI2 with 4,4′-trimethylene dipyridine (tmp) or 3,3′-azobispyridine in THF gives two adducts [HgI2(tmp)]n (1) and [HgI2(ázobpy)]n (2). 1 has a wave-shaped polymeric structure originated from anti–anti conformation of the tmp ligands. 2 possesses zigzag structures interacting each other via Hg⋯I bond to form a 3D supramolecule structure. Their optical limiting threshold was determined to be 0.8 and 0.4 J cm−2, which is comparable to those of many heterothiometallates.
Co-reporter:Linke Li, Bingyi Chen, Yinglin Song, Gang Li, Hongwei Hou, Yaoting Fan, Liwei Mi
Inorganica Chimica Acta 2003 Volume 344() pp:95-101
Publication Date(Web):20 February 2003
DOI:10.1016/S0020-1693(02)01316-6
In this paper a new Cd-4,4′-bpy co-ordination framework formulated as [Cd(en)(NO3)2(4,4′-bpy)]n has been prepared and characterized by single crystal X-ray diffraction. The polymer exhibits a zigzag chain structure bridged by 4,4′-bpy. Cd atoms are in a distorted octahedronal coordination environment, binding to two NO3−, one μ2-en and two 4,4′-bpy. In the solid state structure, all the zigzag chains are connected by two kinds of NH⋯O hydrogen bonds to lead to a three-dimensional network. The polymer also exhibits strong NLO refraction behavior, its n2 value is 6×10−18 m2 W−1 in a 2.2×10−4 mol dm−3 DMF solution, and gives self-focusing effect. The susceptibilities χ(3) and the hyperpolarizability |γ| value were calculated to be 1.5×10−11 esu and 1.7×10−29 esu, respectively. The |γ| is comparable to those of the known cluster compounds, and better than those observed in other compounds, such as ferrocene derivatives, Group 10 metal alkynyl polymers and some octopolar alkynylruthenium complexes.A new Cd-4,4′-bpy co-ordination framework [Cd(en)(NO3)2(4,4′-bpy)]n has been prepared and characterized by single crystal X-ray diffraction. The polymer has a zigzag chain structure bridged by 4,4′-bpy, and exhibits strong NLO refraction properties. Its hyperpolarizability |γ| value is 1.7×10−29 esu, which is better than those observed in other compounds, such as ferrocene derivatives, Group 10 metal alkynyl polymers.
Co-reporter:Xiangru Meng, Gang Li, Hongwei Hou, Huayun Han, Yaoting Fan, Yu Zhu, Chenxia Du
Journal of Organometallic Chemistry 2003 Volume 679(Issue 2) pp:153-161
Publication Date(Web):15 August 2003
DOI:10.1016/S0022-328X(03)00516-3
Novel two-dimensional layered lanthanide(III)-ferrocenedicarboxylate coordination polymers {[M(η2-O2CFcCO2-η2)(μ2-η2-O2CFcCO2-η2-μ2)0.5(H2O)2]·mH2O}n (Fc=(η5-C5H4)Fe(η5-C5H4), M=Tb3+, m=2, 1; M=Eu3+, m=2, 2; M=Y3+, m=1, 3) with trapezium-shaped units and one-dimensional wave-shaped Cd(II)-ferrocenedicarboxylate polymer {[Cd(η2-O2CFcCO2-η2)(H2O)3]·4H2O}n (4) have been prepared and structurally characterized by single crystal diffraction. In polymers 1–3, each central metal ion (Tb(III), or Eu(III) or Y(III)) is located in a pseudo-capped-tetragonal prism coordination geometry, and ferrocenedicarboxylate anion ligands have two coordination modes (bidentate-chelating mode and tridentate-bridging mode). The magnetic behaviors for 1 and 2 are studied in the temperature range of 5.0–300 K. The results show that the paramagnetic behavior of 2 is mainly due to the effective spin–orbital coupling between the ground and excited states through the Zeeman perturbation, and the weak magnetic interaction between Eu3+ centers can be observed. In addition, compared with sodium ferrocenedicarboxylate, the fluorescent intensities of the polymers 1–4 are enhanced in the solid state.Novel two-dimensional layered lanthanide(III)-ferrocenedicarboxylate polymers {[M(η2-O2CFcCO2-η2)(μ2-η2-O2CFcCO2-η2-μ2)0.5(H2O)2]·mH2O}n (M=Tb3+, m=2, 1; M=Eu3+, m=2, 2; M=Y3+, m=1, 3) and one-dimensional wave-shaped Cd(II)-ferrocenedicarboxylate polymer {[Cd(η2-O2CFcCO2-η2)(H2O)3]·4H2O}n (4) have been prepared. The magnetic behaviors for 1 and 2 were studied in the temperature range of 5.0–300 K. In addition, compared with free ligand sodium ferrocenedicarboxylate, the fluorescent intensities of the polymers 1–4 are enhanced in solid state.
Co-reporter:Jianhua Qin, Bing Ma, Xiao-Fei Liu, Hong-Lin Lu, Xi-Yan Dong, Shuang-Quan Zang and Hongwei Hou
Journal of Materials Chemistry A 2015 - vol. 3(Issue 24) pp:NaN12697-12697
Publication Date(Web):2015/05/06
DOI:10.1039/C5TA00322A
A water-stable fluorescent microporous metal–organic framework (MOF), [Tb(L)(OH)]·x(solv) (1), has been designed and successfully synthesized under a combination of hydro/solvothermal and ionothermal conditions (H2L = 5-(4-carboxyphenyl)pyridine-2-carboxylate). The crystal structure reveals that complex 1 consists of cubane-shaped tetranuclear terbium building units, which are further bridged by the multicarboxylate ligands to give a (3,12)-connected topology with the point symbol (420·628·818)(43)4. More importantly, the excellent hydrolytic stability allows it to be used in an aquatic system, which is highly desirable for practical applications. Activated 1 shows high selectivity and sensitivity towards nitroaromatic explosives in both aqueous and vapor phases. The sizes of the pore windows (11.2 × 11.2 Å2) in 1, which are larger than the sizes of the selected nitroaromatics, could permit easy diffusion of analytes inside the channel, keeping the electron rich framework and electron deficient analytes in close proximity.
Co-reporter:Jie Wei, Yan Lei, Huimin Jia, Jiamei Cheng, Hongwei Hou and Zhi Zheng
Dalton Transactions 2014 - vol. 43(Issue 29) pp:NaN11338-11338
Publication Date(Web):2014/05/16
DOI:10.1039/C4DT00827H
Silver oxides (Ag2O and AgO) have attracted increasing attention as potential solar cell materials for photovoltaic devices due to their ideal bandgap and non-toxicity. In order to eliminate the complicated synthesis and harsh reaction conditions (e.g. high temperature, high vacuum, high energy input, electron beam instrumentation) required by most synthetic strategies, we developed a very facile dry chemical approach to directly prepare AgxO species on the ITO substrate by taking advantage of a UV-O3 surrounding in a controlled way. We systematically investigated the effects of relative humidity, reaction temperature, and the silver deposition technique on the formation of silver oxide (AgO or Ag2O) thin films. A possible synthetic mechanism for the formation of AgO and Ag2O is proposed. More importantly, we have designed and successfully fabricated novel inorganic hybrid Ag2O/Bi2O3 heterojunction thin films for the first time which exhibit significantly improved photocurrent compared with pure Bi2O3 films.
Co-reporter:Jian-Hua Qin, Bing Ma, Xiao-Fei Liu, Hong-Lin Lu, Xi-Yan Dong, Shuang-Quan Zang and Hongwei Hou
Dalton Transactions 2015 - vol. 44(Issue 33) pp:NaN14603-14603
Publication Date(Web):2015/07/01
DOI:10.1039/C5DT02054A
Reactions of lanthanide nitrate, 1,3,5-benzenetrisbenzoic acid (H3BTB) and [RMI]Br ionic liquids (RMI = 1-alkyl-3-methylimidazolium; R = ethyl, propyl, butyl, amyl, or hexyl), gave rise to two novel lanthanide metal–organic frameworks (Ln-MOFs) [Ln(BTB)H2O], where Ln = Eu 1, Tb 2. In addition to helping solubilise the starting materials under the reaction conditions there is evidence that [RMI]Br itself can play a structure directing role and is intimately involved in template ordering in [Ln(BTB)H2O], even though neither the [RMI]+ cation nor the Br− anion is occluded into the ultimate structure. 1 and 2 are isostructural and consist of infinite rod-shaped lanthanide-carboxylate building units which are further bridged by trigonal-planar BTB ligands to give noninterpenetrated open 3D frameworks featuring a (6,6)-connected topology with the point symbol (44·67·84)(48·67). Importantly, the strong emission of 1 and 2 dispersed in water prompted us to explore their application for detection of different nitroaromatics in an aquatic system. 1 and 2 show similar selectivity and sensitivity towards the presence of trace amounts of nitroaromatic analytes in the aqueous phase, showing potential as explosive sensors.
Co-reporter:Haijuan Du, Wenli Zhang, Chaohai Wang, Yunyin Niu and Hongwei Hou
Dalton Transactions 2016 - vol. 45(Issue 6) pp:NaN2628-2628
Publication Date(Web):2015/12/18
DOI:10.1039/C5DT04508H
A new nanocrystalline inorganic–organic hybrid semiconductor [(BV)2(Ag5Br9)]n (1) with an intriguing windmill-like 1-D [Ag5Br9]nn− polymeric chain was assembled. Great efforts were devoted to investigate its semiconducting properties and applications, such as photoluminescence, emission decay lifetime, waste water purification, electrochemistry behavior and dielectric properties.
Co-reporter:Yue Tong, Xiao Han, Chao Huang, Zhichao Shao, Li'an Guo, Yazhen Wang, Jie Ding and Hongwei Hou
Dalton Transactions 2016 - vol. 45(Issue 9) pp:NaN3705-3705
Publication Date(Web):2016/02/08
DOI:10.1039/C6DT00067C
Several new isostructural lanthanide metal–organic frameworks {[Ln3(L)4(OH)(H2O)2]·DMAC}n (Ln = Tb (1), Gd (2), Eu (3), Gd0.81Tb0.10Eu0.09 (4) and Gd0.75Tb0.18Eu0.07 (5)) were designed and prepared. Excitingly, samples 1, 3, 4 and 5 showed reversible Al3+-induced chromaticity switching as well as reversible Fe3+-induced emission switching.
Co-reporter:Huarui Wang, Chao Huang, Yanbing Han, Zhichao Shao, Hongwei Hou and Yaoting Fan
Dalton Transactions 2016 - vol. 45(Issue 18) pp:NaN7785-7785
Publication Date(Web):2016/03/29
DOI:10.1039/C6DT00726K
The rigid and planar tetracarboxylic acid 5,5′-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid (H4L), incorporating a triazole group, has been used with no or different pyridine-based linkers to construct a family of d10 coordination polymers, namely, {[H2N(CH3)2]3[Cd3(L)2(HCOO)]}n (1), {[Cd2(L)(py)6]·H2O}n (2), {[H2N(CH3)2] [Cd2(L)(HCOO)(H2O)4]}n (3), {[Zn(H2L)]·H2O}n (4), and {[Zn(H2L)(4,4′-bipy)0.5]·C2H5OH·H2O}n (5) (py = pyridine, 4,4′-bipy = 4,4′-bipyridine). 1 constructs a 3D porous network containing two kinds of channels: one is filled with coordinated HCOO− anions, and the other with [H2N(CH3)2]+ cations. The framework of 1 can be described as a rare (5,6,7)-connected net with the Schläfli symbol of (412·5·62)(45·53·62)2(48·53·68·82)2. The Cd(II) ions in 2 are connected through the carboxylate ligands to form a 2D layer, with aperture dimensions of ∼15.1 Å × 16.2 Å. The network of 3 features a 3D (3,4)-connected (6·8·10)2(6·83·102) topology. A 3D network with the (42·6·83) topology of 4 possesses an open 1D channel with the free volume of 29.2%. 5 is a 2D layer structure with the (42·63·8)(42·6) topology. The fluorescence lifetime τ values of 1–5 are on the nanosecond timescale at room temperature. In particular, central-metal exchange in 2 leads to a series of isostructural M(II)–Cd frameworks [M = Cu (2a), Co (2b), Ni (2c)] showing improved catalytic activity for the synthesis of 1,4,5,6-tetrahydropyrimidine derivatives. Based on this, a plausible mechanism for the catalytic reaction has been proposed and the reactivity–structure relationship has been further clarified.
Co-reporter:Shengli Huang, Xiaoxia Li, Xianju Shi, Hongwei Hou and Yaoting Fan
Journal of Materials Chemistry A 2010 - vol. 20(Issue 27) pp:NaN5699-5699
Publication Date(Web):2010/06/10
DOI:10.1039/C0JM00605J
Using 2D grids of [Cd(btx)2Cl2]n1 and [Co(btx)2Cl2]n2 (btx = 1,4-bis(triazol-1-ylmethyl)benzene) as parent complexes, with terminal dicarboxylic ions as anion substitutors and bridge ligands, we synthesized extended structures of 3D polymeric networks with {[Cd2(btx)2(tp)2]·H2O}n3 and [Co3(btx)4(tp)3(H2O)4]n4 (tp = terephthalic ion) with Schläfli symbols (423·65) and (44·62)(48·67), respectively. The complete cation exchanged products Cu2+-1, Cu2+-3 and Cd2+-4 were obtained by immersing 1, 3 and 4 into corresponding aqueous solutions of MCl2 (M = Cu2+ or Cd2+). Interestingly, fluorescence studies on the pre- and post-exchanged materials compounds indicate that central metal ions have great influence on the fluorescence signal of the materials compounds, and play more important roles than skeleton structures.
Co-reporter:Jin Jin, Weiyin Wang, Yanhua Liu, Hongwei Hou and Yaoting Fan
Chemical Communications 2011 - vol. 47(Issue 26) pp:NaN7463-7463
Publication Date(Web):2011/05/31
DOI:10.1039/C1CC12142A
The first hexagonal octadecanuclear Ag macrocycle [Ag18(TTTMB)12](NO3)18·30H2O has been hydrothermally synthesized. The outside and inner diameters of the unprecedented architecture are about 27.72(13) Å and 15.37(7) Å, respectively. This complex displays a huge increase in the intensity and lifetime of phosphorescence with decreasing temperature.
Co-reporter:Huijun Li, Hongchang Yao, Erpeng Zhang, Yanyuan Jia, Hongwei Hou and Yaoting Fan
Dalton Transactions 2011 - vol. 40(Issue 37) pp:NaN9393-9393
Publication Date(Web):2011/08/15
DOI:10.1039/C1DT10822K
The crystal structures and magnetic properties of two novel polyclusters {[Cu3(tci)2(H2O)2]·12H2O}n (1) and {[Cu3(tci)2(H2O)2]·6H2O}n (2) (tci = tris(2-carboxyethyl) isocyanurate) are investigated. The X-ray crystallographic analysis reveals that they contain interesting infinite alternating chains of dinuclear paddle-wheel copper and mononuclear copper units arranged in ABBA magnetism exchange mode. Variable-temperature magnetic susceptibility measurements on the two polyclusters show strong antiferromagnetism couplings between copper ions with exchange interactions J = −181.4 cm−1, zj′ = −0.31 cm−1 for 1, J = −170 cm−1, zj′ = −0.42 cm−1 for 2. With the aim of studying magneto-structural correlation, we synthesized a three-dimensional polymer [Cu3(tci)2(py)4(H2O)2]n (3) based on isolated dinuclear cluster and mononuclear copper units. Fitting the susceptibility data yielded J = −176.1 cm−1, zj′ = −0.084 cm−1 for 3.
Co-reporter:Lu Liu, Jie Ding, Ming Li, Xiaofeng Lv, Jie Wu, Hongwei Hou and Yaoting Fan
Dalton Transactions 2014 - vol. 43(Issue 33) pp:NaN12799-12799
Publication Date(Web):2014/06/17
DOI:10.1039/C4DT01080A
A series of novel CdII coordination complexes, formulated as {[Cd(btbb)0.5(p-phda)]·H2O}n (1), [Cd(btbb)0.5(oba)]n (2), {[Cd2(btbb)(m-bdc)2(H2O)]·2H2O}n (3), {[Cd(btbb)0.5(btec)0.5(H2O)]·2H2O}n (4), [Cd(btbb)0.5(o-bdc)]n (5) and {[Cd2(btbb)(bptc)(H2O)]·4H2O}n (6) (btbb = 1,4-bis(2-(4-thiazolyl)benzimidazol-1-ylmethyl)benzene, H2phda = phenylenediacetic acid, H2oba = 4,4′-oxybis(benzoic acid), m-H2bdc = 1,3-benzenedicarboxylic acid, H4btec = 1,2,4,5-benzenetetracarboxylate, o-H2bdc = 1,2-benzenedicarboxylic acid, H4bptc = 3,3′,4,4′-benzophenone tetracarboxylic acid), have been obtained by solvothermal/hydrothermal reactions for the exploration of efficient photocatalytic degradation of organic dye pollutants. Complex 1 features a 6-connected 3D pcu α-Po primitive cubic topology net with the point symbol 412·63. Interestingly, complexes 2, 3 and 5 contain left- and right-handed helical chains (2: a 2-fold interpenetrating 3D architecture with {412·63}-pcu topology network; 3: a (3,6)-connected net with a vertex symbol (42·54·66·7·82)(4·62); 5: a (3,4)-connected 3,4L83 topology net with point symbol (42·6)(42·63·8)). Complex 4 exhibits a (3,4)-connected 3,4T48 topology net with point symbol (84·102)(8·102), while complex 6 possesses a (3,5)-connected 3,5L2 topology with the point symbol (42·6)(42·67·8). Furthermore, the photophysical studies indicate that the relatively narrow optical energy gaps of complexes 1–6 (<2.30 eV) calculated from the diffuse reflectivity spectra reflect their outstanding semiconductive nature. The photocatalytic properties of complexes 1–6 were studied in detail, and the results demonstrate their good photocatalytic activities in methylene blue (MB) degradation reactions, especially for complexes 3, 4 and 6 (3: 91.4%, 4: 92.7%, 6: 86.7%).
Co-reporter:Chao Huang, Jie Wu, Chuanjun Song, Ran Ding, Yan Qiao, Hongwei Hou, Junbiao Chang and Yaoting Fan
Chemical Communications 2015 - vol. 51(Issue 51) pp:NaN10356-10356
Publication Date(Web):2015/05/07
DOI:10.1039/C5CC02432C
Upon single-crystal-to-single-crystal (SCSC) oxidation/reduction, reversible structural transformations take place between the anionic porous zeolite-like CuI framework and a topologically equivalent neutral CuICuII mixed-valent framework. The unique conversion behavior of the CuI framework endowed it as a redox-switchable catalyst for the direct arylation of heterocycle C–H bonds.
Co-reporter:Zhichao Shao, Chao Huang, Xiao Han, Huarui Wang, Angran Li, Yanbing Han, Kai Li, Hongwei Hou and Yaoting Fan
Dalton Transactions 2015 - vol. 44(Issue 28) pp:NaN12838-12838
Publication Date(Web):2015/05/29
DOI:10.1039/C5DT01457C
A series of 2D layered isostructural coordination complexes {[M3(L)2(H2O)6]·H2O}n (M = Mn (1), Mn0.7Co0.3 (2), Mn0.5Co0.5 (3), Mn0.3Co0.7 (4), and Co (5), respectively, H3L = 1-aminobenzene-3,4,5-tricarboxylic acid) have been synthesized under hydrothermal conditions, and applied to catalyze the reaction of degenerating organic dyes under visible light irradiation. The photocatalytic results indicate that complex 5 exhibits good photocatalytic properties in the presence of H2O2, while 1 can restrain the photodegradation of organic dyes. Remarkably, when Mn ions are gradually replaced by Co ions in the complexes, the photocatalytic activities of 1–5 turn from inhibition to promotion, which is a controllable regulation of photocatalytic properties via changing metal ions. Moreover, by using novel magnetic analysis methods and diffuse-reflectance UV/Vis spectra analysis methods, we explain the influence of central metal ions on the photocatalytic performance.
Co-reporter:Huarui Wang, Jianhua Qin, Chao Huang, Yanbing Han, Wenjuan Xu and Hongwei Hou
Dalton Transactions 2016 - vol. 45(Issue 32) pp:NaN12716-12716
Publication Date(Web):2016/07/11
DOI:10.1039/C6DT02321E
Eleven water-stable isostructural mono/bimetallic lanthanide coordination polymers (Ln-CPs) {[EuxTb1−x (HL)(H2O)3]·H2O}n (x = 1.0 (1), 0.9 (3), 0.8 (4), 0.7 (5), 0.6 (6), 0.4 (7), 0.3 (8), 0.2 (9), 0.1 (10), 0.05 (11), 0 (2), H4L = 5,5′-(1H-2,3,5-triazole-1,4-diyl)diisophthalic acid) with uncoordinated Lewis basic triazole sites within the pores were prepared. The Ln-CPs represented by 1 showed a rapid and drastic emission quenching induced by external Fe3+ and Cr3+ cations and CrO42− and CO32− anions in aqueous solution. In addition, because of the comparable emission intensities of Eu3+ and Tb3+ ions, bimetallic CP 8 can be used as a ratiometric luminescent sensor for organic solvent molecules. Moreover, the luminescent color of the 8 sensor in pyridine and in other guest solvents undergoes obvious changes that can be clearly distinguished by the naked eye.
Co-reporter:Junhong Fu, Huijun Li, Yajuan Mu, Hongwei Hou and Yaoting Fan
Chemical Communications 2011 - vol. 47(Issue 18) pp:NaN5273-5273
Publication Date(Web):2011/03/31
DOI:10.1039/C1CC10251F
{[Cu6(TTTMB)8(OH)4(H2O)6]·8(NO3)·34.5H2O}n can reversibly transform to {[Cu6(TTTMB)8I3]·9I·26H2O}n upon a single crystal to single crystal process. The transformation is accompanied by the formation of weak Cu2+⋯I− interactions and changes in the coordination numbers, as well as modulation in their properties.
Co-reporter:Qi Feng, Yuanyuan Li, Lili Wang, Chen Li, Jinmin Wang, Yuanyuan Liu, Kai Li and Hongwei Hou
Chemical Communications 2016 - vol. 52(Issue 15) pp:NaN3126-3126
Publication Date(Web):2016/01/18
DOI:10.1039/C5CC10423H
A series of 4-N,N-dimethylaminoaniline salicylaldehyde Schiff-base derivatives (DAS) were facilely prepared. They exhibit typical AIE properties with various fluorescence emissions and high fluorescence quantum yields in an aggregated state. DAS exhibit unique pH-dependent optical properties, which indicated their potential applications in pH sensing.
Co-reporter:Zhouqing Xu, Qiang Wang, Huijun Li, Wei Meng, Yi Han, Hongwei Hou and Yaoting Fan
Chemical Communications 2012 - vol. 48(Issue 46) pp:NaN5738-5738
Publication Date(Web):2012/04/23
DOI:10.1039/C2CC31590D
[8+12]-metallamacrocycle-based 3D frameworks {[Cu4(pbt)2(SO4)2(DMF)2(CH3OH)]·7H2O·DMF}n (1) and [12]-macrocycle 3D {[Cu2(pbt)(SO4)(DMSO)(CH3OH)2]·5H2O·CH3OH}n (2) have been obtained. Both complexes display antiferromagnetic couplings and high catalytic activity in the oxidative coupling reaction of 1-ethynylbenzene and oxazolidin-2-one.
Co-reporter:Jian-Hua Qin, Hua-Rui Wang, Qi Pan, Shuang-Quan Zang, Hongwei Hou and Yaoting Fan
Dalton Transactions 2015 - vol. 44(Issue 40) pp:NaN17651-17651
Publication Date(Web):2015/09/08
DOI:10.1039/C5DT03026A
Seven Mn(II) coordination polymers, namely {[Mn2(ptptp)Cl2(H2O)3]·H2O}n (1), {[Mn(μ-ptptp)3]2[Mn3(μ3-Cl)]2}·2Cl·16H2O (2), {[Mn2(ptptp)(ip)2(H2O)3]·H2O}n (3), {[Mn2(ptptp)(5-CH3-ip)2(H2O)3]·H2O}n (4), {[Mn4(ptptp)(5-Br-ip)3(H2O)3]·4H2O}n (5), {[Mn2(ptptp)(Hbtc)(H2O)2]·2H2O}n (6) and {[Mn2(ptptp)(tdc)(H2O)2]·1.5H2O}n (7), have been prepared based on multidentate N-heterocyclic aromatic ligands and bridging carboxylate ligands (H2ptptp = 2-(5-{6-[5-(pyrazin-2-yl)-1H-1,2,4-triazol-3-yl]pyridin-2-yl}-1H-1,2,4-triazol-3-yl)pyrazine; R-isophthalic acids, H2ip-R: R = –H (3), –CH3 (4), –Br (5); H3btc = trimesic acid (6); H2tdc = thiophene-2,5-dicarboxylic acid (7)), in order to further probe the multiple roles of [RMI]Br ionic liquids in the hydro/solvothermal synthesis (RMI = 1-alkyl-3-methylimidazolium, R = ethyl, or propyl, or butyl). The successful syntheses of complexes 2–6 suggest that in hydro/solvothermal synthesis the addition of a small amount of [RMI]Br plays a crucial role. Complex 1 exhibits single right-handed helices constructed by ptptp ligands and Mn(II) ions. Complex 2 possesses octanuclear helicate structures in which two propeller-shaped [Mn(μ-ptptp)3]4− units embrace two [Mn3(μ3-Cl)]5+ cluster cores inside. Complexes 3 and 4 are isostructural and display a 1D double chain formed by two kinds of pseudo meso-helices: (Mn-ptptp)n and (Mn-5-R-ip)n. Complex 5 has a 2D structure containing 1D Mn(II) ion chains formed through carboxylates and [ptptp]2−-N,N bridges. Complex 6 shows a 2D structure formed by a meso-helix (Mn-ptptp)n and the partly deprotonated Hbtc ligands. Complex 7 features a heterochiral [2 + 2] coaxially nested double-helical column formed by using the outer double-helices (Mn-ptptp)n as a template to encapsulate the inner double-helices (Mn-tdc)n with opposite orientation. All complexes were characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, single-crystal X-ray crystallography and powder X-ray diffraction. The magnetic properties of 1–7 were also investigated.
Co-reporter:Lili Wang, Yuanyuan Li, Xuejiao You, Kui Xu, Qi Feng, Jinmin Wang, Yuanyuan Liu, Kai Li and Hongwei Hou
Journal of Materials Chemistry A 2017 - vol. 5(Issue 1) pp:NaN72-72
Publication Date(Web):2016/11/02
DOI:10.1039/C6TC03791G
Luminescent molecules with photochromic properties show strong potential in molecular switches, molecular logic gates, photo-controllable materials, bio-imaging, anti-counterfeiting, photo-patterning, etc. However, research is still scarce in such molecules exhibiting reversible photo-controllable color and fluorescence changes in solid states, which is due to the aggregation-caused quenching (ACQ) effect of most luminogens. In this work, a reversible photochromic molecule (1) with aggregation-induced emission (AIE) properties was developed. Compound 1 exhibits typical AIE properties as a result of restricted intramolecular rotation (RIR) and excited-state intramolecular proton transfer (ESIPT) processes. As a photochromic molecule, compound 1 shows reversible color and fluorescence changes upon UV light irradiation with good fatigue resistance. More importantly, the conversion rate from its irradiated form to its initial form is controllable by temperature and long wavelength light irradiation, which makes it suitable for photo-patterning materials with erasable properties.
