Co-reporter:Cheng-Peng Li;Hang Zhou;Si Wang;Hong-Han Yuan;Su-Zhen Zhang
Chemical Communications 2017 vol. 53(Issue 35) pp:4767-4770
Publication Date(Web):2017/04/27
DOI:10.1039/C7CC02005H
A cationic Ag(I) coordination polymer with 1D nanoporous channels (ca. 1.22 nm diameter) shows the selective and complete removal of carcinogenic dye Acid Red 26 from aqueous solution upon the size-exclusion and charge-matching effect.
Co-reporter:Cheng-Peng Li;Hang Zhou;Si Wang;Jing Chen;Zhong-Liang Wang
Chemical Communications 2017 vol. 53(Issue 66) pp:9206-9209
Publication Date(Web):2017/08/15
DOI:10.1039/C7CC04527A
The single-crystal to single-crystal (SC–SC) transformation from a 1D coordination chain to a 3D coordination network, which is triggered by both solvent and anion exchanges, has been revealed to suffer from a tandem mechanism as proved by isolation of the intermediate state. The resulting porous crystalline material shows a high efficiency for the capture of dichromates (207 mg g−1) via the SC–SC anion-exchange.
Co-reporter:Di-Ming Chen, Nan-Nan Zhang, Chun-Sen LiuZhi-Hao Jiang, Xing-Dong Wang, Miao Du
Inorganic Chemistry 2017 Volume 56(Issue 5) pp:
Publication Date(Web):February 20, 2017
DOI:10.1021/acs.inorgchem.6b03170
A unique channel-type metal–organic framework (MOF) built up from mixed square-planar Co4(μ2-OH)4(μ4-OH) and cuboidal Co4(μ3-OH)4 clusters with an isonicotinic acid ligand has been successfully fabricated that demonstrates the highest specific surface area and high H2 uptake capacities among all of the cobalt(II) isonicotinic acid frameworks reported so far.
Co-reporter:Cheng-Peng Li, Bo-Lan Liu, Lei Wang, Yue Liu, Jia-Yue Tian, Chun-Sen Liu, and Miao Du
ACS Applied Materials & Interfaces 2017 Volume 9(Issue 8) pp:
Publication Date(Web):February 7, 2017
DOI:10.1021/acsami.6b16757
To avoid the instability and inefficiency for anion-exchange resins and layered double-hydroxides materials, we present herein a flexible coordination network [Ag(L243)](NO3)(H2O)(CH3CN) (L243 = 3-(2-pyridyl)-4-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole) with superefficient trapping capacity for permanganate, as a group-7 oxoanion model for radiotoxic pertechnetate pollutant. Furthermore, a high-throughput screening strategy has been developed based on concentration-gradient design principle to ascertain the process and mechanism for anion exchange. Significantly, a series of intermediates can be successfully isolated as the qualified crystals for single-crystal X-ray diffraction. The result evidently indicates that such a dynamic material will show remarkable breathing effect of the three-dimensional host framework upon anion exchange, which mostly facilitates the anion trapping process. This established methodology will provide a general strategy to discover the internal secrets of complicated solid-state reactions in crystals at the molecular level.Keywords: anion exchange; capture mechanism; crystal transformation; dynamic porous material; high-throughput screening;
Co-reporter:Di-Ming Chen, Jia-Yue Tian, Chun-Sen Liu and Miao Du
Chemical Communications 2016 vol. 52(Issue 54) pp:8413-8416
Publication Date(Web):24 May 2016
DOI:10.1039/C6CC02359B
Incorporating the in situ formed size-matching molecular building blocks (MBBs) into the open channels will remarkably improve the robustness and gas sorption performance of an evacuated metal–organic framework. As a result, such MBBs can transfer the open metal sites from the framework walls to the channel centers and separate the large channels into multiple smaller voids, leading to a molecular sieving effect and high-performance gas-separation of the modified material.
Co-reporter:Di-Ming Chen, Jia-Yue Tian, Min Chen, Chun-Sen Liu, and Miao Du
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 28) pp:18043-18050
Publication Date(Web):June 24, 2016
DOI:10.1021/acsami.6b04611
A moisture-stable three-dimensional (3D) metal–organic framework (MOF), {(Me2NH2)[Zn2(bpydb)2(ATZ)](DMA)(NMF)2}n (1, where bpydb = 4,4′-(4,4′-bipyridine-2,6-diyl)dibenzoate, ATZ = deprotonated 5-aminotetrazole, DMA = N,N-dimethylacetamide, and NMF = N-methylformamide), with uncoordinated N-donor sites and charged framework skeleton was fabricated. This MOF exhibits interesting structural dynamic upon CO2 sorption at 195 K and high CO2/N2 (127) and CO2/CH4 (131) sorption selectivity at 298 K and 1 bar. Particularly, its CO2/CH4 selectivity is among the highest MOFs for selective CO2 separation. The results of Grand Canonical Monte Carlo (GCMC) simulation indicate that the polar framework contributes to the strong framework–CO2 binding at zero loading, and the tetrazole pillar contributes to the high CO2 uptake capacity at high loading. Furthermore, the solvent-responsive luminescent properties of 1 indicate that it could be utilized as a fluorescent sensor to detect trace amounts of nitrobenzene in both solvent and vapor systems.
Co-reporter:Min Chen, Hui Zhao, E. Carolina Sañudo, Chun-Sen Liu, and Miao Du
Inorganic Chemistry 2016 Volume 55(Issue 8) pp:3715-3717
Publication Date(Web):March 29, 2016
DOI:10.1021/acs.inorgchem.5b02716
Two isomorphic 3-D complexes with the formulas [M3(TPTA) (OH)2(H2O)4]n (M = Ni for 1 and Co for 2; H4TPTA = [1,1′:4′,1″-terphenyl]-2′,3,3″,5′-tetracarboxylic acid) have been synthesized and magnetically characterized. Complexes 1 (NiII) and 2 (CoII) have the same 1-D rod-shaped inorganic SBUs but exhibit significantly different magnetic properties. Complex 2(CoII) is a 3-D arrangement of a 1-D CoII single-chain magnet (SCM), while complex 1(NiII) exhibits weak coupling.
Co-reporter:Xi Wang, Min Chen, and Miao Du
Inorganic Chemistry 2016 Volume 55(Issue 13) pp:6352
Publication Date(Web):June 22, 2016
DOI:10.1021/acs.inorgchem.6b00760
Two isostructural the-type DyIII coordination networks were successfully constructed based on a pair of analogous tribenzoate bridging ligands with phenyl and triazinyl central spacers. Notably, the active triazinyl group can obviously enhance the capability and selectivity of CO2 sorption for the porous framework.
Co-reporter:Di-Ming Chen, Jia-Yue Tian, Chun-Sen Liu and Miao Du
CrystEngComm 2016 vol. 18(Issue 21) pp:3760-3763
Publication Date(Web):03 May 2016
DOI:10.1039/C6CE00709K
By virtue of unique planar [Co6(μ3-OH)4] cluster units, a new microporous isonicotinate-based framework with high thermal and framework stabilities was achieved. The guest-free framework demonstrates high capacity and selectivity for C2H2 relative to CO2 and CH4 at room temperature, which was further understood by GCMC simulation.
Co-reporter:Dr. Cheng-Peng Li;Qi Chen;Yu-Hai Mu ;Dr. Miao Du
ChemPlusChem 2016 Volume 81( Issue 8) pp:857-863
Publication Date(Web):
DOI:10.1002/cplu.201600155
Abstract
Solvothermal reactions of a bifunctional ligand 4-(2-ethyl-1H-imidazol-1-yl)benzoic acid (2-Heiba) with Cu(NO3)2 and Cu(OAc)2 afforded two coordination polymers, [Cu3(2-eiba)4(NO3)2]⋅5 DMF (1; DMF= N,N-dimethylformamide) and [Cu(2-eiba)2] (2), respectively, which show a twofold interpenetrated 3D network and 2D+2D3D polycatenated architecture. Complex 1 is a potential luminescent detector for nitrobenzene and FeIII ions, whereby strong antiferromagnetic interactions are also found between the CuII centers.
Co-reporter:Dr. Cheng-Peng Li;Qi Chen;Yu-Hai Mu ;Dr. Miao Du
ChemPlusChem 2016 Volume 81( Issue 8) pp:
Publication Date(Web):
DOI:10.1002/cplu.201600329
Co-reporter:Min Chen, Hui Zhao, Chun-Sen Liu, Xi Wang, Heng-Zhen Shi and Miao Du
Chemical Communications 2015 vol. 51(Issue 27) pp:6014-6017
Publication Date(Web):25 Feb 2015
DOI:10.1039/C5CC00018A
A pair of supramolecular isomers of Co(II)-based metal–organic frameworks can be directionally constructed in virtue of solvent templates, which show diverse bilayer networks and lattice packing with the same Co3 SBUs and organic linkers. The two porous materials show distinct gas sorption behaviors at different temperatures, especially their CO2 sorption selectivity.
Co-reporter:Cheng-Peng Li, Jing Chen, Chun-Sen Liu and Miao Du
Chemical Communications 2015 vol. 51(Issue 14) pp:2768-2781
Publication Date(Web):21 Oct 2014
DOI:10.1039/C4CC06263A
Reactions in the solid state, especially single-crystal-to-single-crystal (SC–SC) transformations, provide an appealing pathway to obtain target crystalline materials with modified properties via a solvent-free green chemistry approach. This feature article focuses on the progress to date in the context of coordination supramolecular systems (CSSs), especially coordination polymers (CPs) or metal–organic frameworks (MOFs), which show interesting dynamic natures upon exposure to various exogenous stimuli, including concentration, temperature, light and mechanical force, as well as their synergic effect. In essence, dynamic CSSs normally possess crucial crystalline-reactive characteristics: (i) metal ions or clusters with unstable or metastable electronic configurations and coordination geometries; (ii) organic ligands bearing physicochemically active functional groups for subsequent reactions; (iii) polymeric networks of high flexibility for structural bending, rotation, swelling, or shrinking; (iv) guest moieties to be freely exchanged or eliminated by varying the environmental conditions. The significant changes in catalytic, sorption, magnetic, or luminescent properties accompanied by the structural transformations will also be discussed, which reveal the proof-of-concept thereof in designing new functional crystalline materials.
Co-reporter:Cheng-Peng Li, Jing Chen, Yu-Hai Mu and Miao Du
Dalton Transactions 2015 vol. 44(Issue 24) pp:11109-11118
Publication Date(Web):05 May 2015
DOI:10.1039/C5DT00420A
Seven Zn(II) coordination complexes with 5-halonicotinic acids (HL-X, X = F, Cl, or Br) have been synthesized with different synthetic approaches, including layer diffusion or stirring method in an ambient environment and solvothermal synthesis at 100 °C. Assembly of HL-F with Zn(II) under different conditions will yield the same 2D network of [Zn(L-F)2]n (1). Interestingly, three distinct complexes, a 3D framework {[Zn2(L-Cl)4(H2O)](H2O)6}n (2) and two 2D pseudo-polymorphic isomers {[Zn(L-Cl)2](H2O)1.5}n (3) and {[Zn2(L-Cl)4](H2O)}n (4) can be obtained by reacting HL-Cl with Zn(II) under layer diffusion, stirring, and solvothermal conditions, respectively. Furthermore, replacing the –Cl substituent with –Br on the HL-X ligand will also afford three diverse coordination assemblies of 3D {[Zn2(L-Br)4(H2O)](CH3OH)2.5}n (5), mononuclear [Zn(HL-Br)2(H2O)4][L-Br]2 (6), and 2D {[Zn(L-Br)2](H2O)1.15}n (7) depending on the synthetic pathways. Beyond the significant influence of the synthetic approach, which will lead to the formation of various crystalline products, the halogen substitution effect of HL-X ligands on the coordination motifs has also been demonstrated. In addition, thermal stability and fluorescence for these crystalline materials will be presented.
Co-reporter: Miao Du;Xi Wang;Dr. Min Chen;Dr. Cheng-Peng Li;Jia-Yue Tian;Zhuo-Wei Wang; Chun-Sen Liu
Chemistry - A European Journal 2015 Volume 21( Issue 27) pp:
Publication Date(Web):
DOI:10.1002/chem.201590121
Co-reporter:Zhuo-Wei Wang;Dr. Min Chen; Chun-Sen Liu;Xi Wang;Hui Zhao; Miao Du
Chemistry - A European Journal 2015 Volume 21( Issue 48) pp:17215-17219
Publication Date(Web):
DOI:10.1002/chem.201502615
Abstract
A unique AlIII-based metal–organic framework (467-MOF) with two types of square channels has been designed and synthesized by using a flexible tricarboxylate ligand under solvothermal conditions. 467-MOF exhibits superior thermal and chemical stability and, moreover, shows high CO2 sorption selectivity over H2, with a selectivity, based on the ideal adsorbed solution theory (IAST) of approximately 45 at 273 or 293 K. Furthermore, its solvent-dependent photoluminescence makes it an applicable sensor in the detection of nitrobenzene explosives through fluorescence quenching.
Co-reporter: Miao Du;Xi Wang;Dr. Min Chen;Dr. Cheng-Peng Li;Jia-Yue Tian;Zhuo-Wei Wang; Chun-Sen Liu
Chemistry - A European Journal 2015 Volume 21( Issue 27) pp:9713-9719
Publication Date(Web):
DOI:10.1002/chem.201500457
Abstract
A promising alternative strategy for designing mesoporous metal–organic frameworks (MOFs) has been proposed, by modifying the symmetry rather than expanding the length of organic linkers. By means of this approach, a unique MOF material based on the target [Zn8(ad)4] (ad=adeninate) clusters and C3-symmetric organic linkers can be obtained, with trigonal microporous (ca., 0.8 nm) and hexagonal mesoporous (ca., 3.0 nm) 1D channels. Moreover, the resulting 446-MOF shows distinct reactivity to transition and lanthanide metal ions. Significantly, the transmetalation of CoII or NiII on the ZnII centers in 446-MOF can enhance the sorption capacities of CO2 and CH4 (16–21 %), whereas the impregnation of EuIII and TbIII in the channels of 446-MOF will result in adjustable light-emitting behaviors.
Co-reporter:Miao Du ; Cheng-Peng Li ; Min Chen ; Zhi-Wei Ge ; Xi Wang ; Lei Wang ;Chun-Sen Liu
Journal of the American Chemical Society 2014 Volume 136(Issue 31) pp:10906-10909
Publication Date(Web):July 14, 2014
DOI:10.1021/ja506357n
Selective adsorption and separation of CO2 are of great importance for different target applications. Metal–organic frameworks (MOFs) represent a promising class of porous materials for this purpose. Here we present a unique MOF material, [Cu(tba)2]n (tba = 4-(1H-1,2,4-triazol-1-yl)benzoate), which shows high CO2 adsorption selectivity over CH4/H2/O2/Ar/N2 gases (with IAST selectivity of 41–68 at 273 K and 33–51 at 293 K). By using a critical point dryer, the CO2 molecules can be well sealed in the 1D channels of [Cu(tba)2]n to allow a single-crystal X-ray analysis, which reveals the presence of not only Cδ+—H···Oδ− bonds between the host framework and CO2 but also quadrupole–quadrupole (CO2δ−···δ+CO2) interactions between the CO2 molecules. Furthermore, [Cu(tba)2]n will suffer divergent kinetic and thermodynamic hydration processes to form its isostructural hydrate {[Cu(tba)2](H2O)}n and a mononuclear complex [Cu(tba)2(H2O)4] via single-crystal to single-crystal transformations.
Co-reporter:Miao Du, Min Chen, Xiao-Gang Yang, Jiong Wen, Xi Wang, Shao-Ming Fang and Chun-Sen Liu
Journal of Materials Chemistry A 2014 vol. 2(Issue 25) pp:9828-9834
Publication Date(Web):15 Apr 2014
DOI:10.1039/C4TA00963K
Stability is a critical issue in practical applications of metal–organic frameworks (MOFs). These materials are usually destroyed by heating or exposure to chemicals, which cause them to reduce or even lose their porous nature. We report here a mesoporous 437-MOF material with perfect 1-D hexagonal channels of ca. 3 nm pore size, which shows both high thermal and chemical stability. The gas sorption capacity of desolvated 437-MOF can be improved by activating the material at higher temperatures. Remarkably, optimum porosity is achieved using a combined approach of heating the sample in boiling water followed by further heating. This unexpected observation can be ascribed to the synergistic effects of the external and internal surfaces of the porous crystalline material. An exploration of the possible applications of this material in supercapacitors shows a great potential for activated 437-MOF to be used as an electrode material as a result of its high surface area (ca. 2400 m2 g−1), hierarchical pore structure, and the pseudocapacitor contribution provided by doping with In.
Co-reporter:Min Chen, E. Carolina Sañudo, Erika Jiménez, Shao-Ming Fang, Chun-Sen Liu, and Miao Du
Inorganic Chemistry 2014 Volume 53(Issue 13) pp:6708-6714
Publication Date(Web):June 17, 2014
DOI:10.1021/ic500490x
Five isostructural lanthanide–organic coordination frameworks with a unique 3-D 5-connected (47.63)(43.65.82) network, namely, [Ln(phen)(L)]n (Ln = Dy for 1, Gd for 2, Ho for 3, Er for 4, and Tb for 5), have been prepared based on bridging 5-hydroxyisophthalic acid (H3L) and chelating 1,10-phenanthroline (phen) coligand. Significantly, the Dy(III) complex 1 is an organized array of single-molecular magnets (SMMs), with frequency-dependent out-of-phase ac susceptibility signals and magnetization hysteresis at 4 K. Further analysis of the magnetic results can reveal that the SMM behavior of 1 should arise from the smaller ferromagnetic interaction between the Dy(III) ions. Complex 1 was also characterized by X-ray absorption spectra, which give the clear X-ray magnetic circular dichroism signal.
Co-reporter:Miao Du, Min Chen, Xi Wang, Jiong Wen, Xiao-Gang Yang, Shao-Ming Fang, and Chun-Sen Liu
Inorganic Chemistry 2014 Volume 53(Issue 14) pp:7074-7076
Publication Date(Web):July 2, 2014
DOI:10.1021/ic5005374
This work presents a mesoporous DyIII metal–organic framework with two types of void cages (diameters: 4.4 and 2.8 nm), which can efficiently adsorb a variety of chemical pollutants, including toxic metals, iodine, and formaldehyde.
Co-reporter:Cheng-Peng Li, Jing Chen, Peng-Wen Liu and Miao Du
CrystEngComm 2014 vol. 16(Issue 28) pp:6433-6443
Publication Date(Web):13 Mar 2014
DOI:10.1039/C4CE00187G
Nine 5-methylnicotinate (L–CH3−) coordination complexes, namely, {[Ni(L–CH3)2(H2O)2](H2O)}n (1), [Ni2(L–CH3)4(H2O)]n (2), Ni(HL–CH3)2Cl2 (3), [Cd2(L–CH3)2(SO4)(H2O)6]n (4), [Cd(L–CH3)2(H2O)]n (5), {[Cu(L–CH3)2(H2O)2](H2O)}n (6), {[Co(L–CH3)2(H2O)2](H2O)}n (7), [Mn(L–CH3)2(H2O)2]n (8), and [Pb(L–CH3)2]n (9), were synthesized with different metal salts. For complexes 1–3, the use of different NiII salts (SO42−, OAc−, or Cl−) leads to three distinct coordination motifs, including a 3D lvt framework, a 3D self-interpenetrating (3·4·5)(32·43·53·6·74·82) network, and a mononuclear species, respectively. For CdII, two different 1D chain complexes can be assembled from HL–CH3 with CdSO4 (4) and Cd(OAc)2 or CdCl2 (5). However, such an anion effect has not been observed for the CuII (6), CoII (7), MnII (8), and PbII (9) complexes, which show a 3D lvt network for 6 and 7, a 2D (4,4) layer for 8, and a 3D (3,5)-connected (4·62)(4·67·82) network for 9. These results demonstrate that the diverse coordination motifs for 1–9 (from 0D, 1D, 2D, to 3D) can be effectively adjusted by the metal-ligating tendency and metal-dependent counter-anion effect. Thermal stability and solid-state fluorescence have also been investigated.
Co-reporter:Miao Du, Cheng-Peng Li, Chun-Sen Liu, Shao-Ming Fang
Coordination Chemistry Reviews 2013 Volume 257(7–8) pp:1282-1305
Publication Date(Web):April 2013
DOI:10.1016/j.ccr.2012.10.002
The rational construction of coordination polymers (CPs), normally existing as infinite crystalline lattices extended from inorganic vertices and organic struts, essentially benefits from the development of crystal engineering strategies. In this review, we summarily comment on the key advances in the design of CPs using mixed-ligand synthetic strategy and discuss the relationship between the specifically selected mixed organic ligands and the resulting CPs. Significantly, fine tuning on the structural features of organic ligands, such as spacers, positional isomers, and substituents, can lead to a delicate regulation of the diverse network structures of CPs. Additionally, such mixed-ligand coordination assemblies may also be heavily affected by metal ion, synthetic route, and some other external stimuli such as solvent and pH condition, etc. The advantages of mixed-ligand systems as promising approaches to construct CPs-based crystalline materials with interesting structures and useful properties will also be demonstrated.Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (227 K)Download as PowerPoint slideHighlights► Mixed-ligand synthetic strategy for the design and construction of coordination polymers has been summarized. ► Coordination frameworks with mixed ligands can be rationally modulated by modifying the traits of organic tectons and other external stimuli. ► Structural aesthetics and promising properties of mixed-ligand coordination polymers have been illustrated.
Co-reporter:Sheng-Chun Chen, Zhi-Hui Zhang, Qun Chen, Li-Qun Wang, Juan Xu, Ming-Yang He, Miao Du, Xiao-Ping Yang and Richard A. Jones
Chemical Communications 2013 vol. 49(Issue 13) pp:1270-1272
Publication Date(Web):07 Dec 2012
DOI:10.1039/C2CC36538C
Three isomeric water-soluble and light-stable silver(I) coordination polymers with a fluorinated carboxylate ligand were prepared by template-controlled method, which show different 2D polymeric coordination structures with a novel layered inorganic connectivity in the solid state. In water solution, they dissociate into several stable polynuclear silver(I) oligomers and exhibit extraordinary antimicrobial activities against selected bacteria.
Co-reporter:Dong-Sheng Li, Jun Zhao, Ya-Pan Wu, Bin Liu, Liang Bai, Kun Zou, and Miao Du
Inorganic Chemistry 2013 Volume 52(Issue 14) pp:8091-8098
Publication Date(Web):July 2, 2013
DOI:10.1021/ic4007718
Two novel Co(II)-cluster-based coordination polymers—namely, [Co5(μ3–OH)2(1,4-ndc)4(bix)2]n (1) and {[Co8(μ3–OH)4(1,4-ndc)6(btp)(H2O)6]·H2O}n (2)—were prepared by hydrothermal reactions of Co(II) perchlorate with 1,4-naphthalenedicarboxylic acid (1,4-H2ndc) and different N-donor coligands (bix = 1,4-bis(imidazol-1-ylmethyl)benzene and btp = 4,4′-bis(triazol-1-ylmethyl)biphenyl). In 1, 10-connected [Co5(μ3–OH)2(COO)8] clusters are extended by the μ4-1,4-ndc2– and trans-bix ligands to construct a rare, self-penetrating ile framework that can interestingly be regarded as the cross-link of two interpenetrating 6-connected pcu networks. While for 2, [Co8(μ3–OH)4(COO)12] clusters serve as the 8-connected nodes, which are bridged by the μ4/μ5-1,4-ndc2- and trans-btp ligands to afford the highest-connected uninodal self-penetrating (420.68) network based on octacobalt clusters. A synthetic and structural comparison of 1 and 2 demonstrates that the features of auxiliary N-donor ligands play a key role in governing the in situ formed clusters and the final 3-D coordination frameworks. Magnetic susceptibility measurements indicate that complex 1 shows an antiferromagnetic interaction between the adjacent Co(II) ions, whereas 2 displays the dominant antiferromagnetic exchanges in 300–50 K and a ferrimagnetic-like behavior at lower temperatures.
Co-reporter:Zhi-Hui Zhang, Sheng-Chun Chen, Ming-Yang He, Qun Chen, and Miao Du
Crystal Growth & Design 2013 Volume 13(Issue 3) pp:996-1001
Publication Date(Web):February 19, 2013
DOI:10.1021/cg4000445
Four polymeric d10 metal terephthalate complexes incorporating bis-pyridinecarboxamide building blocks were prepared to explore the effect of the central metal ion or the fluorine substituent of the ligand on the topology and entanglement of coordination networks. The combination of ZnII terephthalate with a fluorinated ligand leads to a noninterpenetrated coordination layer with honeycomb (hcb) topology for complex 1. Interestingly, the other three materials display the unusual entangling coordination networks. For 2, the reaction of zinc terephthalate with nonfluorinated ligand affords three-dimensional diamond (dia) architecture of [3 + 3] interpenetration, while the CdII terephthalate complexes 3 and 4 with the two types of bis-pyridinecarboxamide tectons show the isostructural self-penetrating framework with unique 8-connected (417.611) topology.
Co-reporter:Hao-Ling Sun, Rui Jiang, Zongsheng Li, Yong Qiang Dong and Miao Du
CrystEngComm 2013 vol. 15(Issue 9) pp:1669-1672
Publication Date(Web):12 Dec 2012
DOI:10.1039/C2CE26761F
A novel (4,8)-connected scu {[Co(tbe)0.5(H2O)2]·0.5H2O} framework has been built by using a predesigned octahedral node of tetrakis(4-benzoic acid)ethylene. The magneto-structural relation study indicates weak anti-ferromagnetic coupling between metal ions transmitted by syn–anti carboxylate pathway due to the non-planarity of the Co–O–C–O–Co unit.
Co-reporter:Jiong Wen, Xiao-Gang Yang, Wei Guo, Chun-Sen Liu and Miao Du
CrystEngComm 2013 vol. 15(Issue 47) pp:10171-10174
Publication Date(Web):10 Oct 2013
DOI:10.1039/C3CE41828F
Hydrothermal reaction of ZnII salt with cyanuric acid (H3CA) and 1,2,4-triazole (Htz) yields a unique coordination polymer [Zn9(CA)2(μ3-tz)3(μ2-OH)6(μ3-OH)3]n (1), which displays a 3-D (3,18)-connected topological network based on a new type of {Zn18} double-stranded metallacrown.
Co-reporter:Cheng-Peng Li, Jing Chen, Peng-Wen Liu and Miao Du
CrystEngComm 2013 vol. 15(Issue 45) pp:9713-9721
Publication Date(Web):28 Aug 2013
DOI:10.1039/C3CE41116H
Seven CdII coordination polymers have been prepared from CdCl2 and 5-halonicotinic acids (HL–X, X = F or Cl) in different solvent media using a similar layered diffusion method. A pair of polymorphic isomers [Cd(L–F)2]n (1 and 2) can be assembled from CH3CN–H2O and CH3OH–H2O systems, respectively, featuring the 3-D (3,5)-connected (4·62)(4·67·82) network (5-connected node for each CdII ion and 2- or 3-connected linker for the two different types of L–F− ligand) and the 3-D (3,6)-connected ant framework with the point symbol of (4·62)2(44·62·88·10). While in DMF–H2O solvent, a 2-D layered complex [Cd(L–F)Cl(DMF)]n (3) is obtained with the (3,5)-connected net of (3·4·5)(32·4·5·62·74) topology, where the chloride anion is involved in coordination. When the HL–Cl ligand is utilized instead of HL–F, the assembling reactions in CH3CN–H2O and DMF–H2O media lead to the 3-D (3,5)-connected network of [Cd(L–Cl)2]n (4) and the 2-D (3,5)-connected net of [Cd(L–Cl)Cl(DMF)]n (6), which are isostructural to complexes 1 and 3, respectively. [Cd(L–Cl)2(H2O)2]n (5) can be generated from the CH3OH–H2O medium, showing a 2-D (4,4) layered structure, and the similar reaction in the C2H5OH–H2O solvent will produce a 3-D coordination framework {[Cd(L–Cl)2(H2O)0.5](C2H5OH)0.75(H2O)0.25}n (7) with the (3,6)-connected (3·4·5)(32·44·55·62·72) net. These structural divergences can be ascribed to the significant solvent modulation and halogen-substituting effect of 5-halonicotinates. Furthermore, their solid-state properties such as thermal stability and fluorescence have also been investigated.
Co-reporter:Xian-Feng Huang, Zhi-Hui Zhang, Qing-Qing Zhang, Ling-Zhu Wang, Ming-Yang He, Qun Chen, Guo-Qiang Song, Lin Wei, Fan Wang and Miao Du
CrystEngComm 2013 vol. 15(Issue 30) pp:6090-6100
Publication Date(Web):10 May 2013
DOI:10.1039/C3CE40567B
The crystallization of norfloxacin, an antibacterial fluoroquinolone compound, with different benzenedicarboxylic acids yields five novel pharmaceutical salts via molecular recognition. X-ray single-crystal diffraction analyses reveal that these pharmaceutical agents present uniform charge-assistant hydrogen-bonding networks, which are in 1:1 stoichiometry of norfloxacin and dicarboxylate therein (with the exception of that with terephthalate). Unsubstituted benzenedicarboxylates (phthalate in 1, isophthalate in 2, and terephthalate in 3, respectively) are likely to crystallize with norfloxacin without lattice solvents, while the substituted isophthalate moieties (2-aminoisophthalate in 4 and 5-aminoisophthalate in 5) tend to form supramolecular adducts with the inclusion of water. Aromatic stacking interactions are present in all these structures, occurring between the fluoroquinolone and carboxylate phenyl rings (in 1–4) as well as between the fluoroquinolone planes (in 5). Thermal stability and solubility of all crystalline binary adducts have been determined. The effect of carboxylate counterions, substituents, and hydration states on the solubility and dissolution profile of drug salts 1–5 are investigated in pure water and 0.1 M HCl. After the formation of salts, the solubility increases at near neutral pH in almost all cases (except 3), but the order is changed in acidic medium. Phthalic acid shows evidence of a good candidate to enhance the solubility of fluoroquinolone drugs for the solubility of 1 is approximately 39 times as large as that of norfloxacin in pure water and also larger than that of norfloxacin in acidic system. For the isophthalates series, 2 has very poor solubility in 0.1 M HCl (only 0.06 times as that of Nf), while amino substituted isophthalates result in the enhancement of the solubility. Remarkably, crystal packing analyses of these pharmaceutical salts allow a possible correlation between the H-bonding prototypes and the solubility to be established.
Co-reporter:Miao Du, Rahul Banerjee and George K. H. Shimizu
CrystEngComm 2013 vol. 15(Issue 45) pp:9237-9238
Publication Date(Web):22 Oct 2013
DOI:10.1039/C3CE90156D
A graphical abstract is available for this content
Co-reporter:Jian Guo, Cheng-Peng Li, Miao Du
Inorganica Chimica Acta 2013 Volume 395() pp:212-217
Publication Date(Web):30 January 2013
DOI:10.1016/j.ica.2012.10.014
This work presents two pairs of Ag(I) and Cd(II) supramolecular complexes assembled based on two versatile tripyridyltriazole ligands 3,5-bis(2-pyridyl)-4-(4-pyridyl)-1,2,4-triazole (L242) and 3-(2-pyridyl)-4,5-bis(4-pyridyl)-1,2,4-triazole (L244), respectively. All four complexes have been prepared under similar conditions and characterized by elemental analysis, IR, and powder X-ray diffraction techniques. Single-crystal X-ray diffraction indicates that these complexes display the infinite 1-D and 2-D arrays for {[Ag(L242)(CF3COO)](CH3OH)}n (1) and {[Ag2(L242)(CF3COO)2](CH3CN)0.75(H2O)0.25}n (2) as well as discrete dinuclear and tetranuclear coordination patterns for [Cd(L244)I2]2 (3) and [Cd2(L244)2I4(DMF)2]2(DMF)2 (4). In 1 and 3, extended supramolecular architectures are further constructed via aromatic stacking interactions. Structural difference for each pair of complexes can be properly assigned to the significant solvent effect on assembled reactions (CH3OH–H2O vs. CHCl3–CH3CN for 1 and 2 as well as CH3OH–H2O vs. H2O–DMF for 3 and 4). Thermal stability and fluorescence of these complexes have also been investigated.Graphical abstractTwo pairs of distinct Ag(I) and Cd(II) supramolecular complexes have been assembled based on the versatile tripyridyltriazole ligands 3,5-bis(2-pyridyl)-4-(4-pyridyl)-1,2,4-triazole and 3-(2-pyridyl)-4,5-bis(4-pyridyl)-1,2,4-triazole, respectively, which can be well modulated by different solvent media.Highlights► Four Ag(I) and Cd(II) complexes with novel tripyridyltriazole ligands are prepared. ► These complexes show distinct infinite and discrete coordination motifs. ► Significant solvent effect on their coordination assemblies is demonstrated.
Co-reporter:Wei Guo, Albert Escuer, Min Tang, Cheng-Hui Jiang, Miao Du
Inorganica Chimica Acta 2013 Volume 403() pp:142-146
Publication Date(Web):1 July 2013
DOI:10.1016/j.ica.2012.09.031
Assemblies of Cu(II) chloride with dicyanamide (dca) anion and a tripyridyltriazole co-ligand 3,4-bis(2-pyridyl)-5-(3-pyridyl)-1,2,4-triazole (L223) under different ligand-to-metal ratios produce two coordination polymers {[Cu5(L223)4(dca)10](H2O)2}n (1) and [Cu(L223)(dca)Cl]n (2), displaying distinct 1D double-chain array and 3D chiral dia network, respectively. Weak antiferromagnetic exchanges are observed in both coordination polymers.Graphical abstractTwo distinct 1D and 3D Cu(II) coordination polymers can be assembled based on dicyanamide anion and a tripyridyltriazole tecton, through simply adjusting the ligand-to-metal ratios, in both of which weak antiferromagnetic interactions are observed between the metal ions.Highlights► Ligand-to-metal ratio dependent assembly of two Cu(II) coordination polymers can be achieved. ► The two coordination polymers show distinct 1D double-chain array and 3D chiral dia network. ► Weak antiferromagnetic interactions between the Cu(II) ions are observed in both systems.
Co-reporter:Cheng-Peng Li, Jian Guo, Miao Du
Inorganic Chemistry Communications 2013 Volume 38() pp:70-73
Publication Date(Web):December 2013
DOI:10.1016/j.inoche.2013.09.064
•Two isostructural 3D coordination polymers can be constructed from CdII or ZnII perchlorate and a multidentate tripyridyltriazole ligand.•The open coordination framework possesses 1D channels for including guest perchlorate.•Both materials show the exclusive anion-exchange selectivity to acetate.Two isostructural 3D coordination polymers (CPs) {[M(L242)2](ClO4)2}n (MII = CdII for 1 and ZnII for 2) have been constructed from metal perchlorates and a tripyridyltriazole ligand 4-(4-pyridyl)-3,5-bis(2-pyridyl)-1,2,4-triazole (L242). The host framework of each CP comprises two interpenetrating lvt topological networks. Three types of 1D channels with different chirality (achirality and left-handed or right-handed helicity) are observed to hold the perchlorate guest anions. Interestingly, both CPs materials have the exclusive and irreversible anion-exchange behaviors for acetate (OAc−), which however, are unavailable to chloride (Cl−), fluoroborate (BF4−), or nitrate (NO3−) anion. CPs 1 and 2 also show ligand-based solid-state fluorescent emissions at room temperature.This work presents two isostructural 3D CdII and ZnII coordination polymers consisting of open host coordination framework and perchlorate anionic guest, which show the selective anion-exchange behaviors toward acetate in an irreversible way.
Co-reporter:Chun-Sen Liu, Xiao-Gang Yang, Min Hu, Miao Du and Shao-Ming Fang
Chemical Communications 2012 vol. 48(Issue 60) pp:7459-7461
Publication Date(Web):08 Jun 2012
DOI:10.1039/C2CC31905E
A 3-D metal–organic framework constructed from the linear trimetallic [Cd2NaO6(H2O)6] secondary building units (SBUs) and a long flexible 6,6’-dithiodinicotinate tecton is presented, which has a 6-connected (46.69)-hxg network with high-symmetry hexagonal geometries.
Co-reporter:Lu-Fang Ma ; Min-Le Han ; Jian-Hua Qin ; Li-Ya Wang
Inorganic Chemistry 2012 Volume 51(Issue 17) pp:9431-9442
Publication Date(Web):August 21, 2012
DOI:10.1021/ic3012537
Five new MnII coordination polymers, namely [Mn2(tbip)2(bix)] (1), [Mn3(tbip)3(bix)2] (2), [Mn3(tbip)2(Htbip)2(bib)2]·4H2O (3), [Mn4(tbip)4(bbp)2(H2O)2] (4), and [Mn4(tbip)4(bip)]·2H2O (5), were prepared by hydrothermal reactions of Mn(II) acetate with H2tbip (5-tert-butyl isophthalic acid) in the presence of different di-imidazolyl coligands (bix =1,4-bis(imidazol-1-ylmethyl)benzene, bib =1,4-bis(imidazol) butane, bbp =1,3-bis(benzimidazol)propane, bip =1,3-bis(imidazol)propane). All complexes were characterized by elemental analysis, IR spectra, thermogravimetric analysis, single-crystal X-ray crystallography, and powder X-ray diffraction. Single crystal X-ray studies show that these coordination polymers contain homometallic clusters varying from dimeric, trimeric, and tetrameric motifs to polymeric chains depending upon the coligands used. Complex 1 has a 3D 6-connected polycatenane network with dinuclear [Mn2O2] secondary building units. Complex 2 possesses a 3D 8-connected structure with trinuclear [Mn3(COO)6] units. Complex 3 shows a 3D pcu net based on trinuclear [Mn3(COO)6] clusters as nodes. Complex 4 features a 3D 8-connected structure constructed from the distorted square-grid tetranuclear [Mn4(μ2-COO)8(μ2-H2O)] units. Complex 5 shows a 3D (4,5,6)-connected net containing 1D μ-O/μ-COO alternately bridged chains. Magnetic susceptibility measurements indicate that complexes 1 and 3–5 show weak antiferromagnetic interactions between the adjacent MnII ions, whereas 2 is a three-spin center homometallic ferromagnetic system.
Co-reporter:Lu-Fang Ma, Jun-Wei Zhao, Min-Le Han, Li-Ya Wang and Miao Du
Dalton Transactions 2012 vol. 41(Issue 7) pp:2078-2083
Publication Date(Web):21 Dec 2011
DOI:10.1039/C1DT11206F
Two novel 3-D coordination polymers with different Cu(II) subunits as nodes and mixed bridging ligands as linkers, namely [Cu5(μ3-OH)2(1,3-bip)2(CH3O-ip)4]n (1) and {[Cu4(1,3-btp)2(CH3O-p)4(H2O)2]·2H2O}n (2) (CH3O-H2ip = 5-methoxyisophthalate, 1,3-bip = 1,3-bis(imidazol)propane, 1,3-btp = 1,3-bis(1,2,4-triazol-1-yl)propane), were prepared under hydrothermal conditions. Complex 1 exhibits a CsCl-type network with [Cu5(μ3-OH)2]8+ clusters acting as nodes, which represents the first 3-D network based on pentanuclear Cu(II) clusters. Complex 2 features a 3-D pillared-layer network with (4,6)-connected (44.62)(44.68.83)-fsc topology, which is a rare example of homometallic coordination polymers constructed by alternate binuclear metal clusters and single metal centres. Variable-temperature magnetic susceptibility measurements show dominant ferromagnetic interactions in the pentanuclear clusters of 1 and strong antiferromagnetic interactions in the dinuclear paddle-wheel units of 2.
Co-reporter:Dong-Sheng Li, Peng Zhang, Jun Zhao, Zi-Fan Fang, Miao Du, Kun Zou, and Yi-Qiang Mu
Crystal Growth & Design 2012 Volume 12(Issue 4) pp:1697-1702
Publication Date(Web):February 27, 2012
DOI:10.1021/cg300036y
This work presents two unique entangled coordination polymers based on square Cd4-building blocks. Complex 1 represents the first example of 2D→ 3D parallel polycatenated architecture constructed from a 4·82-fes net, whereas complex 2 shows an unusual (3,4)-connected self- catenated network that can be viewed as the cross-linking of a 2D + 2D→3D inclined polycatenation.
Co-reporter:Jian-Hua Guo, Wei Guo, Xi Wang, Miao Du
Inorganic Chemistry Communications 2012 Volume 22() pp:77-81
Publication Date(Web):August 2012
DOI:10.1016/j.inoche.2012.05.024
To investigate the effect of positional isomerism of ligands on the construction of coordination polymers, three Cd(II) complexes with tripyridyltriazole tectons and thiocyanate anions have been prepared and characterized, namely, [Cd(L4)(μ-SCN)(SCN)]n (1), [Cd(L5)(SCN)2]n (2), and [Cd(L6)(μ-SCN)2]n (3) (L4 = 3,4-bis(2-pyridyl)-5-(3-pyridyl)-1,2,4-triazole, L5 = 3-(2-pyridyl)-4,5-bis(3-pyridyl)-1,2,4-triazole, and L6 = 3-(2-pyridyl)-4-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole. Crystal structure analysis indicates that the isomeric effect of ligands plays a crucial role in regulating the distinct 1D coordination patterns for 1–3, with the aid of the versatility of thiocyanate anion. The solid-state properties such as thermal stability and fluorescence of 1–3 have also been studied.This work presents the syntheses, crystal structures, and thermal and fluorescent properties of three distinct 1D Cd(II) coordination polymers based on a series of isomeric tripyridyltriazole tectons and thiocyanate anions.Highlights► Three Cd(II) thiocyanate coordination polymers have been synthesized and characterized. ► The isomeric tripyridyltriazole ligands therein show different binding modes. ► The distinct 1D coordination assemblies are determined by positional isomerism of the ligands.
Co-reporter:Jing Chen, Cheng-Peng Li, Jing Shang, Miao Du
Inorganic Chemistry Communications 2012 Volume 15() pp:172-175
Publication Date(Web):January 2012
DOI:10.1016/j.inoche.2011.10.017
Assembly of Cu(ClO4)2·6H2O and 2-(2-pyridyl)-5-(4-pyridyl)-1,3,4-oxadiazole (L) yields a 3-D MOF {[CuL2](ClO4)2(H2O)1/2}n (1). Single crystal X-ray diffraction indicates that 1 has a cationic open coordination framework with lvt topology, where each CuII ion is connected to four L ligands in (η3, μ2) binding mode. The lattice water and perchlorate are accommodated in the 3-D host microporous framework with two types of 1-D channels along different directions. The unusual anion-exchange property is observed for 1, showing the exclusive anion-exchange selectivity with respect to benzoate in an irreversible way.A 3-D metal–organic framework has been constructed from 2-(2-pyridyl)-5-(4-pyridyl)-1,3,4-oxadiazole and CuII perchlorate, which exhibits the exclusive anion-exchange property toward benzoate.Highlights► A 3-D CuII MOF with an unsymmetric ligand 2-(2-pyridyl)-5-(4-pyridyl)-1,3,4-oxadiazole is prepared. ► The cationic coordination network has an open lvt topological framework with the inclusion of perchlorate and water. ► This MOF material shows the exclusive anion-exchange selectivity to benzoate.
Co-reporter:Sheng-Chun Chen, Zhi-Hui Zhang, Huan Xu, Hai-Bo Gao, Rui-Rui Qin, Qun Chen, Ming-Yang He, Miao Du
Inorganic Chemistry Communications 2012 Volume 15() pp:180-184
Publication Date(Web):January 2012
DOI:10.1016/j.inoche.2011.10.019
Two distinct coordination polymers [Cu(Fbix)2(NO3)2]n (1) and {[Cu(Fbix)2(NO3)2]·6H2O}n (2) have been prepared from the reactions of CuII nitrate with a flexible fluorinated ligand 2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-yl-methyl)benzene (Fbix) under different solvents. Single crystal X-ray diffraction reveals that 1 displays a 1-D double-chain structure containing the Fbix with gauche conformation whereas 2 has a 2-D rhombic grid network containing the Fbix with anti conformation. Their spectroscopic, thermal, and fluorescence properties have also been investigated.Two new CuII coordination polymers [Cu(Fbix)2(NO3)2]n (1) and {[Cu(Fbix)2(NO3)2]·6H2O}n (2) have been obtained through the solvent-regulated assembly of CuII nitrate and a flexible fluorinated ligand 2,3,5,6-tetrafluoro-1,4-bis(imidazol-1-yl-methyl)benzene (Fbix). Their significant structural discrepancy of the 1-D (for 1) and 2-D (for 2) networks results from the conformational isomerism of the Fbix ligands.Highlights► A novel flexible fluorinated bis(imidazole) building block is used to creat two CuII coordination polymers. ► Structural discrepancy of the 1-D and 2-D networks results from the varied conformations of the ligands. ► Thermal behavior and solid-state fluorescent emissions are available.
Co-reporter:Dr. Cheng-Peng Li;Jing-Min Wu ;Dr. Miao Du
Chemistry - A European Journal 2012 Volume 18( Issue 39) pp:12437-12445
Publication Date(Web):
DOI:10.1002/chem.201200909
Abstract
A series of nine coordination polymers {[Cd(L)2(solvent)x](solvent)y}n have been prepared from Cd(NO3)2 and 5-bromonicotinic acid (HL) in different solvents through a layered diffusion method. By using CH3OH/H2O at different volume ratios of 1:1 and 1:3, a one-dimensional (1D) coordination species (1 a) and a three-dimensional (3D) (3,6)-connected framework (2 a⋅g1) can be obtained. A similar self-assembly process in C2H5OH/H2O or H2O/1,4-dioxane gives 2 a⋅g2 or 2 a⋅g3, which are isomorphic to 2 a⋅g1 but with different lattice solvents. Replacement of the mixed solvents with DMF/H2O (v/v 1:1 or 1:3) also gives a 1D chain complex (1 b) or a 3D microporous framework (2 b⋅g1). Similarly, MOF 2 b⋅g2 can be assembled from CH3CN/H2O as an isomorphic solvate of 2 b⋅g1. Significantly, the 3D MOF families of 2 a⋅gn and 2 b⋅gn are supramolecular isomers even though they are topologically equivalent. Also, if a mixture of CH3OH/CH2Cl2 (v/v 1:1 or 3:1) is used, a pair of distinct MOFs (3 a⋅g) and (3 b) are generated as pseudo-polymorphs that show a two-dimensional (2D) sheet and a 3D coordination framework, respectively. Furthermore, mutual solvent-induced conversions were realized between 1 a and 1 b and between 2 a⋅g1, 2 a⋅g2, and 2 a⋅g3 following the size-dependent rule of the solvent. These results are of great significance in recognizing the solvent effect upon coordination assemblies and their crystal transformations.
Co-reporter:Wei Guo, Xu-Dong Chen, Miao Du, Albert Escuer
Inorganic Chemistry Communications 2012 20() pp: 184-187
Publication Date(Web):
DOI:10.1016/j.inoche.2012.03.004
Co-reporter:Miao Du, Cheng-Peng Li, Jing-Min Wu, Jian-Hua Guo and Gui-Chang Wang
Chemical Communications 2011 vol. 47(Issue 28) pp:8088-8090
Publication Date(Web):17 Jun 2011
DOI:10.1039/C1CC12184G
This work first demonstrates that the robust [Cu2(OOCR)4] unit can be destroyed and reconstructed in the solid state, as observed in water-induced structural interconversion of two distinct coordination polymers with 5-bromonicotinate.
Co-reporter:Cheng-Peng Li and Miao Du
Chemical Communications 2011 vol. 47(Issue 21) pp:5958-5972
Publication Date(Web):08 Apr 2011
DOI:10.1039/C1CC10935A
Solvent effect is a vital subject in the domain of coordination chemistry. In this connection, previous researches mainly focus on the role of solvents in reaction kinetics and thermodynamics during the coordination processes. In virtue of the recent efforts on coordination supramolecular systems, especially coordination polymers or metal–organic frameworks, this feature article aims to demonstrate the solvent effect on regulating such diversiform metallosupramolecular solids, incorporating their crystal growth/assembly, structural modulation, dynamic transformations, and potential applications, which may provide new insights into the rational design and construction of such advanced crystalline materials.
Co-reporter:Cheng-Peng Li, Jing-Min Wu, and Miao Du
Inorganic Chemistry 2011 Volume 50(Issue 19) pp:9284-9289
Publication Date(Web):September 8, 2011
DOI:10.1021/ic200540c
By using different organic acids as additive agents, hydrothermal reactions of AgNO3 with 3,5-bis(2-pyridyl)-4-amino-1,2,4-triazole (2-bpt) lead to formation of two conformational polymorphs of [Ag(2-bpt)](NO3) with bimetallocyclic and 1-D helical coordination patterns. Interconversion between the two supramolecular isomers can be achieved under proper conditions, which will pass through the same intermediate state.
Co-reporter:Miao Du, Zhi-Hui Zhang, Cheng-Peng Li, Jordi Ribas-Ariño, Núria Aliaga-Alcalde, and Joan Ribas
Inorganic Chemistry 2011 Volume 50(Issue 15) pp:6850-6852
Publication Date(Web):June 23, 2011
DOI:10.1021/ic200711e
The reaction of copper(II) nitrate, oxamide, and an angular bridging ligand 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo) under hydrothermal conditions affords a 3D pillared-layer coordination framework {[Cu2(4-bpo)(ox)2](H2O)4}n (1) (ox = oxalate), featuring the unique zeolite-type NiP2 network and interesting properties.
Co-reporter:Shao-Ming Fang, E. Carolina Sañudo, Min Hu, Qiang Zhang, Song-Tao Ma, Li-Ran Jia, Cong Wang, Jia-You Tang, Miao Du, and Chun-Sen Liu
Crystal Growth & Design 2011 Volume 11(Issue 3) pp:811
Publication Date(Web):January 18, 2011
DOI:10.1021/cg1014626
A series of novel three-dimensional (3-D) lanthanide−organic frameworks (LnOFs), with the general formula [Ln2(H-L)3(H2O)4]∞ (Ln = DyIII for 1, GdIII for 2, TbIII for 3, EuIII for 4, and HoIII for 5; H-L = N-protonated 2,6-dihydroxypyridine-4-carboxylate), have been synthesized under hydrothermal conditions. X-ray structural analysis reveals that complexes 1−5 are isostructural and show the unique 3-D coordination framework with a trinodal (3,4,5)-connected (4.62)(42.6)(42.84)(43.6.86)(42.65.83) net topology, in which the H-L ligands adopt different μ4- and μ3-bridging forms. Variable-temperature magnetic susceptibility studies reveal that complexes 1−3 and 5 show ferromagnetic behaviors. Notably, complex 1 (DyIII) is the first instance leading to ferromagnetic coupling for a lanthanide ion through a spin-polarization mechanism. The alternating current (ac) signal observed for 1 and 5 should originate from the long-range ferromagnetic ordering, or it could reflect the splitting of the J multiplet for DyIII or HoIII under a low symmetry crystal field, which would give rise to slow relaxation of the magnetization. Additionally, thermal stability of these crystalline materials has also been investigated by thermogravimetric analysis of mass loss.
Co-reporter:Lu-Fang Ma, Cheng-Peng Li, Li-Ya Wang, and Miao Du
Crystal Growth & Design 2011 Volume 11(Issue 8) pp:3309-3312
Publication Date(Web):July 12, 2011
DOI:10.1021/cg200366a
Hydrothermal reactions of CoII or ZnII acetate with benzene-1,2,3-tricarboxylic acid (H3bta) and 1,2-bi(4-pyridyl)ethane (bpa) afford two unique metal–organic frameworks, in which 1 represents a new type of entangled architecture formed via polycatenane of a pair of (4,4) net with one two-dimensional 3-connected self-interpenetrating pattern, while 2 shows a three-dimensional 4-connected net with a new trinodal topology.
Co-reporter:Sheng-Chun Chen, Zhi-Hui Zhang, Yong-Sheng Zhou, Wei-You Zhou, Yi-Zhi Li, Ming-Yang He, Qun Chen, and Miao Du
Crystal Growth & Design 2011 Volume 11(Issue 9) pp:4190-4197
Publication Date(Web):July 26, 2011
DOI:10.1021/cg200785g
A series of novel metal–organic frameworks (MOFs) have been assembled from PbII and 2,3,5,6-tetrachloro-1,4-benzenedicarboxylic acid (H2BDC-Cl4) by simply adding different alkali metal ions as templates. When only lead nitrate is used, a robust 3D open framework [Pb(BDC-Cl4)(MeOH)2]n (1) with pts topology can be obtained. Incorporating the lighter LiI or NaI ions into the above PbII/BDC-Cl4 system results in two unique isostructural 3D PbII–LiI and PbII–NaI heterometallic frameworks, {[PbLi2(BDC-Cl4)(μ2-OH)2](H2O)}n (2) and [PbNa2(BDC-Cl4)(μ2-OH)2]n (3), which are built from the combination of a 3D rod-packing PbII-carboxylate framework and a 3D NaI–BDC-Cl4 (or LiI–BDC-Cl4) network. When the heavier KI ion is applied, the similar reaction affords a 3D MOF [Pb2(BDC-Cl4)2(DMF)3]n (4), which represents the first pillar-layered PbII coordination network with a (3,5)-connected gra topology. The results illustrate the powerful effect of the alkali-metal templates in MOFs assemblies. The solid-state properties such as thermal stability and luminescence of 1–4 have also been studied.
Co-reporter:Zhi-Hui Zhang, Sheng-Chun Chen, Ming-Yang He, Chao Li, Qun Chen, and Miao Du
Crystal Growth & Design 2011 Volume 11(Issue 12) pp:5171-5175
Publication Date(Web):October 10, 2011
DOI:10.1021/cg200902g
Two chiral d10 metallosupramolecular systems based on an achiral fluorinated Schiff-base ligand have been prepared and characterized. The ZnII complex 1 reveals 21 helical coordination chains with the inclusion of rare water chains of opposite helix in the perpendicular channels, whereas the CdII complex 2 displays the homochiral 1D coordination motifs with 31 symmetry and a 3D supramolecular architecture built by C–H···F interactions.
Co-reporter:Chun-Sen Liu, Miao Du, E. Carolina Sañudo, Jorge Echeverria, Min Hu, Qiang Zhang, Li-Ming Zhou and Shao-Ming Fang
Dalton Transactions 2011 vol. 40(Issue 37) pp:9366-9369
Publication Date(Web):17 Aug 2011
DOI:10.1039/C1DT11039J
A luminescent trinuclear DyIII complex, in which the three DyIII centers with different geometries take a nearly linear disposition, shows the slow magnetic relaxation processes of single ion origin.
Co-reporter:Shao-Ming Fang, Min Hu, Qiang Zhang, Miao Du and Chun-Sen Liu
Dalton Transactions 2011 vol. 40(Issue 17) pp:4527-4541
Publication Date(Web):24 Mar 2011
DOI:10.1039/C0DT00903B
A series of six Ag(I) and Zn(II) coordination polymers, namely, [Ag2(ndc)]∞ (1), {[Zn(ndc)(H2O)](H2O)}∞ (2), {[Ag2(ndc)(4bpy)2][Ag(4bpy)(H2O)](ClO4)(H2O)2}∞ (3), [Zn5(ndc)4(4bpy)2(μ3-OH)2]∞ (4), {[Ag(ndc)(abp)][Ag(abp)](H2O)3}∞ (5), and {[Zn2(ndc)2(abp)(H2O)2](H2O)2}∞ (6), have been prepared by using 2,3-naphthalenedicarboxylic acid (H2ndc), an analogue of 1,2-benzenedicarboxylic acid (H2bdc), and different 4,4′-bipyridyl-like bridging co-ligands 4,4′-bipyridine (4bpy) and trans-4,4′-azobis(pyridine) (abp). The initial complexes 1 and 2 display the unusual two-dimensional (2-D) five-connected (48.62) and the 2-D three-connected (4.82) coordination networks, respectively. When two comparable rod-like linkers 4bpy and abp (with different N,N′-donor separations of the molecular backbones of ca. 7 and 9 Å) are further introduced, two one-dimensional (1-D) complexes 3 and 5, a three-dimensional (3-D) coordination framework 4 with (43)(43.63)(43.65.82)(44.64.82)(410.65) topology and a 2-D 63 layered coordination polymer 6 are constructed. A structural comparison of these complexes with those based on the structurally related bdc ligand suggests that the extended π-conjugated system of ndc with different electronic nature and steric bulk play an important role in constructing the supramolecular architectures for 1–6, which are also regulated by different bridging N-donor co-ligands and metal ions. Moreover, complexes 1–6 show strong solid-state luminescence emissions at room temperature that mainly originate from the intraligand transitions of ndc.
Co-reporter:Cai Li, Dong-Sheng Li, Jun Zhao, Yi-Qing Mou, Kun Zou, Shu-Zhang Xiao and Miao Du
CrystEngComm 2011 vol. 13(Issue 22) pp:6601-6609
Publication Date(Web):04 Oct 2011
DOI:10.1039/C1CE05896G
Four novel Zn(II) and Cd(II) coordination polymers, {[Zn(cmb)(dpa)]·H2O}n (1), {[Zn(cmb)(bpp)]·2.5H2O}n (2), {[Zn(cmb)(bimb)]·3H2O}n (3), and {[Cd2(cmb)2(bimb)]·H2O}n (4) (H2cmb = 2-(carboxymethoxy)benzoic acid; dpa = 4,4′-dipyridylamine; bpp = 1,3-di(4-bipy)propane; bimb = 1,4-bis(imidazol)butane), have been synthesized and characterized by elemental analysis, IR spectra, and X-ray diffraction. Complex 1 exhibits a diamond (dia) framework of four-fold interpenetration (class IIIa). 2 features a rare 1D → 3D polycatenated architecture, which is built from the interlocking of two sets of 1D supramolecular loops running in different directions (almost perpendicular). The 3D crystalline lattice of 3 is constructed through the parallel packing of corrugated 2D 44 (sql) nets. Complex 4 shows a 2D network with the (3,4)-connected (43)2(4 × 104 × 12)(42 × 104) topology, which consists of 1D [Cd(cmb)]n arrays and helical pillars. The results clearly indicate the importance of linking modes of organic ligands and metal centers as well as the auxiliary ligands in the direction of the diverse structures for complexes 1–4. Thermal stabilities and luminescent properties of complexes 1–4 have also been investigated.
Co-reporter:Jing Chen, Cheng-Peng Li and Miao Du
CrystEngComm 2011 vol. 13(Issue 6) pp:1885-1893
Publication Date(Web):14 Dec 2010
DOI:10.1039/C0CE00555J
A series of CdII coordination polymers have been designed and hydrothermally synthesized by using a bent dipyridyl tecton 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) and R-isophthalic acids (H2ip-R; R = –H, –CH3, –OCH3, –tBu, –OH, and –NO2), which exhibit diverse 1D and 2D polymeric coordination networks. The results demonstrate that the substituent effect of R-isophthalates does play a decisive role in directing the structural assemblies of this system, in which secondary interactions such as H-bonding and π⋯π stacking are generally observed to extend the coordination motifs. Notably, the 3-bpo building block shows adaptable conformations (cisoid-I, cisoid-II, and transoid) to facilitate the structural diversity of these complexes. Solid state properties such as thermal stability and fluorescence for these crystalline materials will also be presented.
Co-reporter:Yi-Xia Ren, Mei-Li Zhang, Dong-Sheng Li, Feng Fu, Ji-Jiang Wang, Miao Du, Xiang-Yang Hou, Ya-Pan Wu
Inorganic Chemistry Communications 2011 Volume 14(Issue 1) pp:231-234
Publication Date(Web):January 2011
DOI:10.1016/j.inoche.2010.10.030
A series of 2D Ln-organic coordination frameworks (Ln = Sm3+ for 1, Eu3+ for 2, Tb3+ for 3, and Ho3+ for 4) with (4,6)-connected (44.52)(44.5.6)(44.54.66.7) topology has been constructed, in which 1D zigzag chains and 2D (4,4) networks intertwine mutually into the unusual 1D and 2D mixed self-weaving patterns. Interestingly, due to the lanthanide contraction effect, the 9-coordinated geometries of the Ln(III) ions gradually transform from triangle tetrakaidecahedron (Sm3+ and Eu3+), to a three-capped triangle prism (Eu3+ and Tb3+), and then to a single-capped anti-square prism (Ho3+).Four Ln-organic coordination frameworks (Ln = Sm3+, Eu3+, Tb3+, and Ho3+) with (4,6)-connected (44.52)(44.5.6)(44.54.66.7) topology are described, in which 1D zigzag chains and 2D (4,4) networks intertwine mutually into an unusual 1D and 2D mixed self-weaving motif. Lanthanide contraction effect is also observed to regulate the coordinated geometries of Ln(III) and the overall 3D lattices.Research Highlights► In this manuscript, we report a series of 2D Ln-organic coordination frameworks (Ln = Sm3+ for 1, Eu3+ for 2, Tb3+ for 3, and Ho3+ for 4) with (4,6)-connected (44.52)(44.5.6)(44.54.66.7) topology, in which 1D zigzag chains and 2D (4,4) networks intertwine mutually into the unusual 1D&2D mixed self-weaving patterns. ► Interestingly, due to the lanthanide contraction effect, the 9-coordinated geometries of the Ln(III) ions gradually transform from triangle tetrakaidecahedron (Sm3+ and Eu3+), to three-capped triangle prism (Eu3+ and Tb3+), and then to single-capped anti-square prism (Ho3+). ► In this point, the 1,3-pda ligand shows an excellent potential in the formation of new Ln3+ coordination frameworks. Also, the 1D&2D mixed self-weaving architectures observed herein provide new perspectives in Ln-carboxylate coordination chemistry. Additionally, thermal stability and fluorescence of these new materials have also been studied. ► These results will enrich the current research of the flexible ligand on constructing Ln-coordination polymers and provide new insights into its application in designing such crystalline materials with desired structures and properties.
Co-reporter:Lu-Fang Ma, Jian-Hua Qin, Min-Le Han, Li-Ya Wang, Miao Du
Inorganic Chemistry Communications 2011 Volume 14(Issue 10) pp:1584-1587
Publication Date(Web):October 2011
DOI:10.1016/j.inoche.2011.06.008
Hydrothermal reaction of Zn(II) acetate, 4,4′-bipyridyl (bpy) and 1,2,3-benzenetricarboxylic acid (H3bta) results in a 3-D coordination framework {[Zn4(bta)2(Hbta)(bpy)3](H2O)3}n (1), which shows the self-penetrating net with a new 4-connected topological prototype and chiral helical character.Hydrothermal reaction of Zn(II) acetate, 4,4′-bipyridyl (bipy) and 1,2,3-benzenetricarboxylic acid (H3bta) results in a 3-D coordination framework, which shows the self-penetrating net with a new 4-connected topological prototype and chiral helical character.Research Highlights► A self-penetrating 4-connected coordination framework with chiral helical features from Zn(II) and mixed organic ligands of H3bta and bipy. ► Complex 1 represents a unique self-penetrating supramolecular pattern with the unprecedented (4.62.83)2(42.62.82) net topology. ► Homochiral crystalline packing of right-handed or left-handed helices was found in the title complex.
Co-reporter:Xi-Jun Ke, Dong-Sheng Li, Miao Du
Inorganic Chemistry Communications 2011 Volume 14(Issue 5) pp:788-803
Publication Date(Web):May 2011
DOI:10.1016/j.inoche.2011.03.018
Self-penetrating coordination networks have recently been demonstrated as an important family of coordination polymers with new topologies and properties. However, the design and control of self-penetrating systems is still an enthralling challenge. In this review, we present the topological types of self-penetrating coordination networks, mainly with single-connectivity, and summarize their designing and constructing strategy.This review discusses the recent development on the design and construction of self-penetrating coordination nets showing various topological types, mainly with single-fold connectivity.Research Highlights►The topological types of self-penetrating coordination networks have been summarized. ►The general tactics for their rational design have been proposed. ►In such area, the next phase of growth has been shown.
Co-reporter:Min Tang, Wei Guo, Su-Zhen Zhang, Miao Du
Inorganic Chemistry Communications 2011 Volume 14(Issue 8) pp:1217-1220
Publication Date(Web):August 2011
DOI:10.1016/j.inoche.2011.04.025
Three novel group IIB metal complexes [Zn3(L4)2Cl6]n (1), {[Cd(L4)Cl2](H2O)}n (2) and [Hg(L4)Cl2]2 (3) with a multidentate N-donor building block 3,4-bis(2-pyridyl)-5-(3-pyridyl)-1,2,4-triazole (L4) have been prepared and characterized. Single crystal X-ray diffraction analysis reveals that 1 is a 2D layered coordination polymer constructed from the linkage of [Zn3(μ-Cl)2] trinuclear units by L4 spacers, 2 shows a 1D coordination pattern with [Cd2(μ-Cl)2] dinuclear units and L4 spacers in pair, whereas 3 has a discrete dinuclear structure. The metal ions used in the assembled processes will dominate the final coordination motifs of these complexes, as also, their extended supramolecular architectures in virtue of various secondary interactions. The solid state properties such as thermal stability and fluorescence of 1–3 are also found to be closely related to the metal centers.Three supramolecular complexes with the group IIB metals and a novel tripyridyltriazole tecton have been synthesized, which exhibit diverse 2D, 1D and dimeric coordination motifs regulated by the metal centers. Their thermal and fluorescent properties have also been discussed.Research highlights► Three group IIB metal complexes with a novel tripyridyltriazole ligand are obtained. ► Their distinct supramolecular lattices are dominated by the nature of metal centers. ► These complexes show different thermal and fluorescent behaviors.
Co-reporter:Cheng-Peng Li, Miao Du
Inorganic Chemistry Communications 2011 Volume 14(Issue 3) pp:502-513
Publication Date(Web):March 2011
DOI:10.1016/j.inoche.2010.12.025
In the past few years, CdII coordination polymers have received much attention due to their diverse structures and interesting properties. This mini-review presents a short summary of the structural styles for such metal-organic networks based on their extended dimensions. Moreover, the influence factors on assemblies and some potential applications will also be commented.The recent progress of CdII coordination polymers is briefly reviewed in the aspects of their diverse structures, adjustable assemblies, and potential applications.Research Highlights► CdII can adopt flexible coordination numbers and geometries. ► CdII coordination polymers show diverse network structures. ► Assembly of CdII coordination polymers may be sensitively influenced. ► CdII coordination polymers have potentially applications.
Co-reporter:Yan Sun, Wei Guo, Miao Du
Inorganic Chemistry Communications 2011 Volume 14(Issue 6) pp:873-876
Publication Date(Web):June 2011
DOI:10.1016/j.inoche.2011.03.015
Assemblies of 3,5-bis(4-pyridyl)-4-(3-pyridyl)-1,2,4-triazole (L3) with Cd(II) in the presence of different pseudohalide anions [N3−, dca (dicyanamide) or SCN−] produce three distinct coordination polymers, i.e. {[Cd5(L3)2(H2O)2(N3)10](CH3OH)2(H2O)4}n (1), [Cd(L3)2(dca)2]n (2) and [Cd(L3)2(SCN)2]n (3). In 1, the N3− anions with three different coordination modes bridge the Cd(II) ions to form 2-D inorganic layers, which are extended by the tridentate L3 ligands to result in a 3-D coordination framework. In 2 and 3, the anion (dca or SCN−) takes the terminal coordination and L3 acts as the bidentate bridge, resulting in 1-D double-strand chain for 2 and double-strand chiral helix for 3. Thermal stability and fluorescence for 1–3 are also presented.This work presents the syntheses, structures, and properties of three Cd(II) coordination polymers with a tripyridyltriazole ligand, which exhibit distinct 3-D coordination network and 1-D double-strand chain or chiral helix arrays directed by the pseudohalide anions.Research highlights► Three distinct Cd(II) coordination polymers are constructed based on a novel tripyridyltriazole tecton. ► Their polymeric structures are regulated by different pseudohalide anions. ► Solid state fluorescent emissions are available at room temperature.
Co-reporter:Zhi-Hui Zhang, Sheng-Chun Chen, Jin-Ling Mi, Ming-Yang He, Qun Chen and Miao Du
Chemical Communications 2010 vol. 46(Issue 44) pp:8427-8429
Publication Date(Web):11 Oct 2010
DOI:10.1039/C0CC03173A
Entangled nets in coordination compounds with both self-penetrating and interpenetrating structural features have been first constructed by using a flexible bis-pyridinecarboxamide and isophthalate or 5-methylisophthalate. Distinct entangled systems showing both 3-fold interpenetration and polyrotaxane can also be obtained by altering the 5-substituents of isophthalate.
Co-reporter:Lu-Fang Ma ; Li-Ya Wang ; Miao Du ;Stuart R. Batten
Inorganic Chemistry 2010 Volume 49(Issue 2) pp:365-367
Publication Date(Web):December 14, 2009
DOI:10.1021/ic9019298
Two unprecedented 2D coordination polymers with 4- and 6-connected topological nets, arising from the different linkages of two adjacent 44 layers, were prepared from CoII, 1,3-bis(4-pyridyl)propane, and different isophthalate tectons.
Co-reporter:Xia Li ; Hao-Ling Sun ; Xiao-Shuo Wu ; Xiao Qiu
Inorganic Chemistry 2010 Volume 49(Issue 4) pp:1865-1871
Publication Date(Web):January 19, 2010
DOI:10.1021/ic902241n
Three porous lanthanide−organic frameworks, [Ln4(OH)4(3-SBA)4(H2O)4]·nH2O [Ln = EuIII (1), n = 10; GdIII (2), n = 10; TbIII (3), n = 8; 3-SBA = 3-sulfobenzoate], have been prepared by a hydrothermal synthesis method. They are isomorphous and crystallize in a tetragonal system with space group P 421c. The structure can be considered to be built up by cubanelike [Ln4(OH)4]8+ secondary building units, which are further connected by 3-SBA to form a 3D coordination framework with 1D pores along the c direction for accommodation of novel T8(3) water tapes or zigzag water chains. Furthermore, in these compounds, the [Ln4(OH)4]8+ units and 3-SBA ligands serve as 12-connected and 3-connected nodes, respectively, resulting in a unique (3,12)-connected framework with the Schläfli symbol of (43)4(420.628.818). The luminescent properties of the EuIII (1) and TbIII (3) complexes have been studied, showing characteristic emissions at room temperature. Variable-temperature magnetic susceptibility studies indicate that the GdIII complex 2 displays weak antiferromagnetic coupling through μ3-OH− pathways.
Co-reporter:Ming-Hua Zeng ; Yan-Ling Zhou ; Mei-Chun Wu ; Hao-Ling Sun
Inorganic Chemistry 2010 Volume 49(Issue 14) pp:6436-6442
Publication Date(Web):June 14, 2010
DOI:10.1021/ic100021f
A new pillared-layer coordination polymer, [Co3(pybz)2(pico)2]n (1; pybz = 4-(pyridin-4-yl)benzoate, pico = 3-hydroxypicolinate), contains rare 2D [Co3(pico)2]n2n+ layers formed by linear cobalt(II) trimers through the unusual μ4-κN,O:κO′-μ2:κO′′-μ2 bridging mode of pico ligands, which are further cross-pillared by exotridentate bridging pybz ligands to form a three-dimensional structure with an unusual uninodal 8-connected body-centered-cubic topology. The bulk magnetic behavior of 1 exhibits ferrimagnetic long-range ordering below 2.6 K, which mainly arises from the cooperative magnetic effect of the intra- and intertrimer arrangements in the 2D magnetic system based on the nature of the exchange modes of μ2-hydroxyl, μ2-carboxylate oxygen, and 1,1,3-μ3-carboxylate bridges.
Co-reporter:Shao-Ming Fang ; Qiang Zhang ; Min Hu ; E. Carolina Sañudo ; Miao Du ;Chun-Sen Liu
Inorganic Chemistry 2010 Volume 49(Issue 20) pp:9617-9626
Publication Date(Web):September 20, 2010
DOI:10.1021/ic101278w
Two CuII coordination complexes {[Cu(ces)(H2O)2](H2O)0.5}n (1) and [Cu15(dhs)6(OH)6(H2O)10](H2O)20 (2) have been synthesized from cis-epoxysuccinic acid (cis-H2ces) and CuII perchlorate under different pH conditions (ces = cis-epoxysuccinate and dhs = 2,3-dihydroxysuccinate), and fully characterized by IR spectra, elemental analyses, as well as single crystal and powder X-ray diffraction techniques. Notably, when the reaction was performed at pH above about 7.4, a one-dimensional (1-D) helical chain complex 1 is formed, whereas a neutral isolated Cu15 nanocluster 2 is generated when the pH value is decreased to the range of about 6.6−7.3, being concomitant with in situ SN2 ring-cleavage reaction of cis-H2ces to form (2S,3S)- and (2R,3R)-H4dhs. Further, extended supramolecular architectures are constructed via secondary interactions in both structures. The magnetic properties of 1 and 2 have also been studied in detail, showing that 1 is an antiferromagnetic helical chain of S = 1/2 spins and 2 possesses an S = 3/2 spin ground state.
Co-reporter:Cheng-Peng Li, Jing Chen, Qian Yu and Miao Du
Crystal Growth & Design 2010 Volume 10(Issue 4) pp:1623-1632
Publication Date(Web):March 1, 2010
DOI:10.1021/cg901188g
A series of silver(I) coordination polymers have been synthesized by the combination of an extended 2,4′-bipyridyl linker trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene (bpe) and different benzenedicarboxyl tectons, including isophthalic acid (H2ip), 5-sulfoisophthalic acid (H3sip), terephthalic acid (H2tp), 2-aminoterephthalic acid (H2ata), and 2-bromoterephthalic acid (H2bta). Single-crystal X-ray diffraction indicates that the structural patterns of these polymeric complexes diversify from two-dimensional (2-D) (3,4,5)-connected (for 2) or 63 (for 3 and 4) layers to three-dimensional (3-D) (10,3)-b (for 1) or 8-nodal self-penetrating (for 5) networks. Interestingly, the AgI centers can show various coordination spheres such as linear, trigonal, tetrahedral, and square-pyramidal geometries. The results clearly reveal that the dicarboxyl building blocks with different dispositions of the carboxyl sites and uncoordinated substituent groups, are the crucial factors for structural assemblies of such extended frameworks. Solid-state properties for these crystalline materials have also been investigated, which display modest thermal stability and strong fluorescent emission at room temperature.
Co-reporter:Cheng-Peng Li, Xiao-Hu Zhao, Xu-Dong Chen, Qian Yu, and Miao Du
Crystal Growth & Design 2010 Volume 10(Issue 12) pp:5034-5042
Publication Date(Web):October 28, 2010
DOI:10.1021/cg100200b
Under different solvothermal reaction conditions I (60 °C for 48 h) and II (140 °C for 72 h), the dipyrazinyl compounds bearing oxadiazole and triazole spacers, that is, 2,5-bis(2-pyrazinyl)-1,3,4-oxadiazole (L1) and 4-amino-3,5-bis(2-pyrazinyl)-1,2,4-triazole (L2), may suffer reversible conversions in the presence of certain metal salts. Other related derivatives such as 3,5-bis(2-pyrazinyl)-1,2,4-triazole-4-yl-N-pyrazinamide (HL4) and pyrazine-2-carboxylic acid (HL0) can also be (in situ) obtained from L1 and L2, respectively, under conditions I and II. Beyond this, N,N′-bis(2-pyrazineamide) (H2L3) can be in situ afforded from both precursors L1 and L2, and thus, may be considered as the potential intermediate during the interconversions. The possible mechanisms and influence factors of these reactions have also been established based on the experimental results. As a result, a variety of crystalline materials (co-crystals and coordination complexes) with attractive supramolecular architectures have been isolated by regulating the reaction conditions well (reaction temperature, metal ion, and even inorganic counteranion).
Co-reporter:Cheng-Peng Li, Jing Chen and Miao Du
CrystEngComm 2010 vol. 12(Issue 12) pp:4392-4402
Publication Date(Web):17 Aug 2010
DOI:10.1039/C003738A
A series of mixed-ligand coordination complexes have been prepared using diffusion method, by reacting the CoII, NiII, ZnII, AgI, CdII, CuII, or PbII nitrate with tetrabromoterephthalic acid (H2tbta) and 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo). These complexes show various 0D, 1D, 2D, and 3D coordination motifs with different geometries of the metal centers, indicating a metal-directed assembly. The synthetic condition will also affect the resulting crystalline products for ZnII species. Crystal structure analysis reveals that secondary interactions such as hydrogen bonding and aromatic stacking will further extend the coordination arrays to diverse supramolecular architectures. All complexes have been characterized by IR, elemental analysis, and powder X-ray diffraction techniques. In addition, the polymeric coordination systems with d10 metal centers show solid-state fluorescent emissions at room temperature, which thus may be applied as potential hybrid luminescent materials.
Co-reporter:Lu-Fang Ma, Bin Liu, Li-Ya Wang, Jiang-Liang Hu and Miao Du
CrystEngComm 2010 vol. 12(Issue 5) pp:1439-1449
Publication Date(Web):22 Dec 2009
DOI:10.1039/B923522C
Five Mn(II) coordination polymers, [Mn3.5(O2N-btb)2(O2N–Hbtb)0.5(2,2′-bipy)2(H2O)4]·1.5H2O (1), [Mn3(O2N-btb)2(4,4′-bipy)3(H2O)2]·2H2O (2), [Mn3(O2N-btb)2(bpe)(H2O)8]·bpe(3), [Mn3(O2N-btb)2(bpa)(H2O)5]·0.5bpa H2O (4) and [Mn3(O2N-btb)2(bpp)2(H2O)4] (5), were prepared by hydrothermal reactions of Mn(II) acetate with O2N–H3btb (O2N–H3btb = 5-nitro-1,2,3-benzenetricarboxylic acid) in the presence of different dipyridyl co-ligands (2,2′-bipy = 2,2′-bipyridyl, 4,4′-bipy = 4,4′-bipyridyl, bpe = 1,2-bi(4-pyridyl)ethene, bpa = 1,2-bi(4-pyridyl)ethane and bpp = 1,3-di(4-pyridyl)propane). Their crystal structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra and TG analyses. Complex 1 shows a 3D (3,5)-connected coordination framework with (42·5)(4·122)(4·5·7)2(42·5·6·7·9·123·13) topology. Notably, the μ7-bridging mode of O2N-btb in 1 has never been found in coordination complexes with 1,2,3-benzenetricarboxylate and its derivatives. Complex 2 exhibits a 3D (4,5)-connected framework with (42·67·8)(64·82)(42·64) topology. Complex 3 shows a 2D 3-connected network with 63 topology. Complex 4 is a 2D (3,4,5)-connected framework with (43)(3·4·5)(3·42·83)(3·4·5·6·72·82·9·10)(43·52·62·72·8) topology, whereas the structure of 5 has a 2D (3,4)-connected (42·6)(42·63·8) framework. The 2D layers in 3 are extended to form a 2-fold interpenetrated 3D supramolecular network, and those in 4 and 5 afford the 3D supramolecular structures via H-bonding interactions. A structural comparison of these complexes demonstrates that the characteristics of auxiliary ligands play a key role in governing the coordination motifs and the final supramolecular lattices. Moreover, the magnetic properties of these Mn(II) complexes were investigated and discussed in detail.
Co-reporter:Lu-Fang Ma, Bin Liu, Li-Ya Wang, Cheng-Peng Li and Miao Du
Dalton Transactions 2010 vol. 39(Issue 9) pp:2301-2308
Publication Date(Web):12 Jan 2010
DOI:10.1039/B920308G
Hydrothermal reactions of mixed ligands 5-methoxyisophthalate (CH3O-H2ip) and dipyridyl with Cu(OAc)2·2H2O afford five new coordination polymers, including {[Cu(CH3O-ip)(bpa)]·H2O}n (1), [Cu2(CH3O-ip)2(bpa)0.5(H2O)]n (2), [Cu2(CH3O-ip)2(bpp)(H2O)]n (3), {[Cu3(CH3O-ip)3(bpp)2(H2O)]·3H2O}n (4) and [Cu4(CH3O-ip)3(bpe)(OH)2]n (5) (bpp = 1,3-di(4-pyridyl)propane, bpa = 1,2-bi(4-pyridyl)ethane, and bpe = 1,2-di(4-pyridyl)ethylene). Compound 1 consists of CH3O-ip anion-bridged 1D CuII chains that are linked by trans-bpa into a 2D layer. Compound 2 is a 2D (4,4) layer that is connected by CH3O-ip anions. The gauche bpa in 2 lies in the cavity and meets the coordination requirement of the paddle-wheel dimeric copper unit. Compound 3 is an extended 3D polythreading network consisting of 2D (4,4) motifs with dangling bpp lateral arms. Compound 4 exhibits a 3D (4,6)-connected self-penetrating (65.8)(614.8) network that is composed of binuclear and mononuclear metal nodes. Compound 5 exhibits a 3D network with the tetranuclear [Cu4(μ3-OH)2]6+ cluster acting as nodes, which is constructed by the interconnection of 2D helical layers via bpe pillars. The results of magnetic determination show that the syn–anti carboxylato bridges in our cases induce a weak antiferromagnetic interaction in 1, and the syn–syn carboxylato bridge in 3 and 4 mediates a strong antiferromagnetic interaction.
Co-reporter:Cheng-Peng Li, Qian Yu, Jing Chen and Miao Du
Crystal Growth & Design 2010 Volume 10(Issue 6) pp:2650
Publication Date(Web):April 20, 2010
DOI:10.1021/cg100144p
A series of CdII, CoII, NiII, and PbII mixed-ligand coordination complexes 1−8 based on 5-sulfoisophthalic acid (H3sip) and the bent dipyridyl ligand 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) or its 4-pyridyl N-donor analogue (4-bpo) have been synthesized and fully characterized by IR spectra, microanalyses, and single crystal and powder X-ray diffraction techniques. The significant pH effect on assembly of the CdII complexes 1−4 has been demonstrated, which leads to the formation of distinct crystalline products, whereas the CoII, NiII, and PbII systems 5−8 are independent to pH condition of the synthetic reaction. Complexes 1−8 display various coordination motifs with different existing forms, conformations, and coordination modes of the organic ligands. Further, extended supramolecular networks are constructed via secondary interactions such as hydrogen-bonding and aromatic stacking. Solid-state properties of thermal stability and fluorescence for these crystalline materials are also presented.
Co-reporter:Miao Du, Qian Wang, Cheng-Peng Li, Xiao-Jun Zhao and Joan Ribas
Crystal Growth & Design 2010 Volume 10(Issue 7) pp:3285
Publication Date(Web):May 26, 2010
DOI:10.1021/cg100465u
This work presents eight coordination assemblies based on divalent metal ions (M = CoII, CuII, ZnII, and CdII), dicyanamide anion (N(CN)2−, dca), and two isomeric bent dipyridyl coligands (L), namely, 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) and 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo). In the resulting crystalline materials, both bpo and dca tectons generally display the bidentate bridging fashion (except in the mononuclear species 5), extending the metal centers to afford diverse one-, two-, and three-dimensional (1-D, 2-D, and 3-D) coordination networks that are not commonly observed in M−dca−L systems. Notably, the inclined polycatenated 2-D → 3-D framework and 3-D polyknotting network with the unique 6-connected (44.611) topology are formed for the CuII and CdII species with dca and 4-bpo. For the polymeric CoII and CuII complexes, very weak antiferromagnetic or ferromagnetic interactions are observed between the metal centers due to the μ1,5-bridging mode of dca, and their magneto-structural correlations have been discussed in detail. The ZnII and CdII complexes show solid-state fluorescent emissions at room temperature.
Co-reporter:Bao-Ming Ji, Dong-Sheng Deng, Ning Ma, Shao-Bin Miao, Xiao-Gang Yang, Li-Guo Ji and Miao Du
Crystal Growth & Design 2010 Volume 10(Issue 7) pp:3060
Publication Date(Web):June 14, 2010
DOI:10.1021/cg100177n
A survey of the Cambridge Structural Database (CSD) indicates that 79% of complexes that contain both imidazole and carboxyl groups generate imidazolium-carboxylate supramolecular heterosynthons rather than carboxyl or imidazole supramolecular homosynthons. In the absence of other competing factors, the occurrence of such heterosynthons is increased to 100%. This observation is further supported by the crystal structures of seven new complexes that contain tris(2-benzimidazylmethyl)amine (TBMA) and a variety of carboxylic acids, including benzoic acid (HBA), p-methoxybenzoic acid (HPMBA), phthalic acid (H2PA), terephthalic acid (H2TPA), isophthalic acid (H2PIA), trimesic acid (H3TMA), and pyromellitic acid (H4PMA). In all seven complexes, (H2TBMA)·(BA)2·DMF (1), (HTBMA)·(PMBA)·(TBMA)·(HPMBA)2·2DMF·H2O (2), (HTBMA)·(H2TBMA)·(HPA)·(PA)·3DMF·H2O (3), (HTBMA)2·(TPA)·2DMF (4), (HTBMA)2·(PIA)·2DMF (5), (H2TBMA)·(HTMA)·0.5DMF·H2O (6), and (HTBMA)2·(H2PMA)·2DMF·H2O (7), proton transfer occurs from acid to aromatic nitrogen of benzimidazole (partial proton transfer for 3, 6, and 7). Analysis of the H-bonding synthons and their effect on crystal packing is also presented in the context of crystal engineering and host−guest chemistry. In the structure of 1, discrete acid/base hexamers are formed via synthons III, V, and VI, while in 2−5, self-recognition via synthons IV, V, and VI results in one-dimensional (1-D) chains, and these structures are extended to high-dimensional architectures (two-dimensional (2-D) structures in 3 and three-dimensional (3-D) structures in 2, 4, and 5) via additional C−H···O, C−H···π and π···π interactions. Interestingly, salts 6 and 7 display the 3-D supramolecular networks via synthons III, IV, V, and VI, which have 1-D channels that are occupied by DMF guests.
Co-reporter:Lu-Fang Ma, Qing-Lei Meng, Cheng-Peng Li, Bo Li, Li-Ya Wang, Miao Du and Fu-Pei Liang
Crystal Growth & Design 2010 Volume 10(Issue 7) pp:3036
Publication Date(Web):June 16, 2010
DOI:10.1021/cg100082f
Eight ZnII and CdII coordination complexes, {[Zn3(nbta)2(bpy)2(H2O)2](H2O)2}n (1), [Zn4(nbta)2(bpe)2(OH)2]n (2), {[Cd3(nbta)2(bpy)5(H2O)2](H2O)6}n (3), {[Cd3(nbta)2(bpe)2(H2O)2](H2O)2}n (4), [Zn2(Hbta)2(bpy)2(H2O)2](H2O) (5), [Zn(bta)(Hbpe)]n (6), [Cd5(bta)2(Hbta)2(bpy)3(H2O)2]n (7), and {[Cd4(bta)2(bpe)2(H2O)4(OH)2](H2O)2}n (8), were prepared via hydrothermal reactions based on H3nbta or H3bta (H3nbta = 5-nitro-1,2,3-benzenetricarboxylic acid and H3bta = 1,2,3-benzenetricarboxylic acid) and the dipyridyl-type coligand 4,4′-bipyridyl (bpy) or 1,2-di(4-pyridyl)ethene (bpe). All complexes were characterized by elemental analysis, IR spectra, and X-ray powder diffraction techniques. Complexes 1−4 all display unusual three-dimensional (3-D) self-penetrating coordination networks. From the topology point of view, complexes 1 and 2 display the 4-connected frameworks with the Schläfli symbols of (4.104.12)2(43.62.8)2(44.62) and (4.62.72.8)2(42.62.7.8), respectively. Complex 3 features an unprecedented 3-nodal network with (3,5,6)-connectivity and the Schläfli symbol of (52.64.72.86.10)(52.65.72.8)2(52.6)2, also exhibiting an intriguing polyrotaxane entangled motif. Complex 4 shows a new 4-connected (42.63.8)4(64.8.10) topology. Different from 1−4, complexes 5−8 based on H3bta all present the non-self-penetrating structural type. Complex 5 possesses binuclear units which are further extended to a two-dimensional (2-D) supramolecular network via extensive H-bonding interactions, showing alternate left- and right-handed helical chains. Complex 6 has a 2-D layered motif generated via H-bonding interactions between the one-dimensional (1-D) coordination chains. Complex 7 shows a 3-D coordination framework, which is constructed from the 2-D metal-carboxylate layers pillared by the rod-like bipy spacers. Complex 8 presents a 2-D net with the [Cd4(μ3-OH)2]6+ clusters as the linking nodes. These results reveal that the existence of the electron-withdrawing -NO2 group in such a tricarboxyl building block plays a critical role in structural direction of the self-penetrating coordination frameworks.
Co-reporter:Shao-Ming Fang, Qiang Zhang, Min Hu, Xiao-Gang Yang, Li-Ming Zhou, Miao Du, and Chun-Sen Liu
Crystal Growth & Design 2010 Volume 10(Issue 11) pp:4773
Publication Date(Web):September 28, 2010
DOI:10.1021/cg100645p
A series of six CdII coordination complexes have been prepared by using naphthalene-2,3-dicarboxylic acid (H2ndc), an analogue of 1,2-benzenedicarboxylic acid (H2bdc), and different N-donor auxiliary co-ligands (chelating or bridging), namely, [Cd(ndc)]∞ (1), {[Cd2(ndc)2(2bpy)2(H2O)2](CH3OH)0.5}2 (2), [Cd2(ndc)2(phen)2]∞ (3), {[Cd(ndc)(4bpy)0.5(H2O)2](H2O)}∞ (4), {[Cd(ndc)(abp)(H2O)](H2O)}∞ (5), and {[Cd(ndc)(bpp)2](H2O)3}∞ (6) (ndc = naphthalene-2,3-dicarboxylate, 2bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, 4bpy = 4,4′-bipyridine, abp = trans-4,4′-azobis(pyridine), and bpp = 1,3-bis(4-pyridyl) propane). The initial complex 1 shows a two-dimensional (2-D) (44.62) coordination network. 2 and 3 possess tetranuclear and one-dimensional (1-D) structures due to the incorporation of auxiliary chelating co-ligands 2bpy and phen, respectively, which are further interlinked via secondary interactions such as hydrogen bonding and aromatic stacking to result in higher-dimensional supramolecular networks. When the 4,4′-dipyridyl-type bridging co-ligands 4bpy, abp, and bpp (with different N,N′-donor separations of the molecular backbones from ca. 7−10 Å) were used as the additional rod-like linkers, a 2-D (3,4)-connected (42.6)(42.63.8) layered coordination net 4 as well as a three-dimensional (3-D) coordination framework 5 with an unusual 4-connected irl topology (42.63.8) and a homochiral 3-D diamond (dia) network 6 were obtained. A structural comparison of these complexes with those based on the structurally related ligand 1,2-benzenedicarboxylate (bdc) suggests that the extended π-conjugated system of ndc with a different electronic nature and steric bulk plays an important role in the construction of supramolecular architectures for 1−6, which can also be well regulated by the different chelating or bridging N-donor co-ligands. Moreover, complexes 1−6 exhibit strong solid-state luminescence emissions at room temperature, which mainly originate from the intraligand π → π* transitions of ndc.
Co-reporter:Cheng-Peng Li, Qian Yu, Zhi-Hui Zhang and Miao Du
CrystEngComm 2010 vol. 12(Issue 3) pp:834-844
Publication Date(Web):29 Oct 2009
DOI:10.1039/B912001G
A new family of ZnII and CdII coordination complexes 1–8 with a multifunctional building block trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene (bpe) have been prepared at ambient conditions in water–methanol solution, by varying the auxiliary benzenedicarboxyl co-ligands from the familiar isophthalic acid (H2ip) and terephthalic acid (H2tp) to their derivatives 5-hydroxylisophthalic acid (H2hip) and tetrabromo-terephthalic acid (H2tbta). Single-crystal X-ray diffraction indicates that these complexes display a variety of coordination motifs, from the discrete mononuclear species (8) to infinite 1-D (1 and 7), 2-D (3, 5, and 6), and 3-D (2 and 4) metal–organic networks. Furthermore, extended supramolecular architectures are constructed for these complexes via predictable secondary interactions such as hydrogen bonding and aromatic stacking. A comprehensive structural analysis and comparison of 1–8 reveals that their crystalline lattices can be properly regulated by a selection of different metal ions (ZnII or CdII) and benzenedicarboxyl co-ligands, as well as the versatile building functionality of the bpe tecton , which can be readily involved in both coordination and secondary interactions. Notably, this work first demonstrates that bpe can also be applied as an angular bridging spacer by using both the 4- and 2-pyridyl groups to construct novel CdII coordination frameworks.
Co-reporter:Dong-Sheng Li, Feng Fu, Jun Zhao, Ya-Pan Wu, Miao Du, Kun Zou, Wen-Wen Dong and Yao-Yu Wang
Dalton Transactions 2010 vol. 39(Issue 48) pp:11522-11525
Publication Date(Web):09 Nov 2010
DOI:10.1039/C0DT00900H
Two unique six-connected self-penetrating coordination polymers with a new (44.610.8) network topology, derived from the cross-linking of two 66-dia subnets, were constructed from NiII or CoII and two types of V-shaped tectons. The NiII complex 1 shows an antiferromagnetic coupling via μ-carboxylate and μ-H2O pathways, whereas the CoII complex 2 exhibits the single-ion behavior in 300–34 K and then a ferromagnetic coupling at lower temperatures.
Co-reporter:Dong-Sheng Li, Ya-Pan Wu, Peng Zhang, Miao Du, Jun Zhao, Cheng-Peng Li and Yao-Yu Wang
Crystal Growth & Design 2010 Volume 10(Issue 5) pp:2037
Publication Date(Web):April 5, 2010
DOI:10.1021/cg100090h
A unique self-penetrating coordination framework with (424.64) network topology is constructed from cage-shaped [Pb6(μ4-O)2(O2C)8] clusters as eight-connected nodes and long V-shaped dicarboxylate backbones as spacers, which interestingly can be regarded as the cross-linking of two interpenetrating six-connected pcu networks.
Co-reporter:Wei Guo, Yu-Yan Yang, Miao Du
Inorganic Chemistry Communications 2010 Volume 13(Issue 7) pp:863-866
Publication Date(Web):July 2010
DOI:10.1016/j.inoche.2010.04.015
Assembly of Cd(II) nitrate with a novel tripyridyltriazole building block 3-(2-pyridyl)-4,5-bis(4-pyridyl)-1,2,4-triazole (L1) and pseudohalide anion dicyanamide (dca) or azide (N3) yields two coordination polymers {[Cd(L1)2(dca)2](H2O)2}n (1) and {[Cd2(L1)(μ1,1-N3)2(μ1,3-N3)(N3)](H2O)1.5}n (2). Single crystal X-ray diffraction analysis indicates that the Cd(II) centers in 1 are bridged by the bidentate L1 ligands to form 1D arrays, which are further extended to a 3D network via hydrogen bonding and aromatic stacking. Significantly, the L1 ligands in 2 display the unusual pentadentate coordination and the azide anions take different μ1,1-, μ1,3-, and unidentate binding modes, interlinking the Cd(II) ions to afford a complicated 3D open framework with the inclusion of lattice water guests. Both complexes exhibit strong solid state fluorescent emissions at room temperature.This work presents two fluorescent Cd(II) coordination polymers based on a novel tripyridyltriazole tecton and different pseudohalide anions (dicyanamide vs. azide), which exhibit distinct 1D double-chain motif and 3D channel-like coordination framework.
Co-reporter:Jian-Hua Guo, Jing Chen, Cheng-Peng Li, Miao Du
Journal of Molecular Structure 2010 Volume 975(1–3) pp:147-153
Publication Date(Web):30 June 2010
DOI:10.1016/j.molstruc.2010.04.008
This work presents six CuII, CoII, and NiII supramolecular complexes assembled from a bent dipyridyl ligand 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) and R-isophthalic acids (R = –CH3 for 5-methylisophthalic acid or R = –OCH3 for 5-methoxyisophthalic acid), which have been prepared using the layer-separation diffusion method and fully characterized by IR, elemental analysis, and powder X-ray diffraction (PXRD) techniques. Single-crystal X-ray diffraction indicates that these complexes show 1-D tube-like (for CuII complexes 1 and 2) or discrete cage-like dinuclear (for CoII and NiII complexes 3–6) coordination patterns. Furthermore, extended 3-D supramolecular architectures are constructed via secondary interactions between the coordination arrays, and three types of packing fashions are observed for the dinuclear species 3–6. Structural diversification for these complexes can be properly attributed to the inherent discrepancy of metal ions and the substituent effect of R-isophthalate tectons.
Co-reporter:Yu-Yan Yang, Wei Guo, Miao Du
Inorganic Chemistry Communications 2010 Volume 13(Issue 10) pp:1195-1198
Publication Date(Web):October 2010
DOI:10.1016/j.inoche.2010.06.049
Coordination polymers [Hg(L2)Cl2]n (1) and {[Hg2(L2)Cl4](DMF)}n (2) have been assembled from Hg(II) chloride and a novel tripyridyltriazole tecton 3,4-bis(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole (L2) in different solvent media. Both complexes have been characterized by IR, microanalysis, powder X-ray diffraction, and thermogravimetric analysis. Single crystal X-ray diffraction indicates that the L2 ligands take the (η3, μ2) and (η4, μ3) binding modes in 1 and 2, respectively, which connect the Hg(II) centers to afford linear and ladder-like 1D arrays. Interestingly, complex 1 exhibits strong solid state fluorescent emission at room temperature due to the intraligand transitions, whereas complex 2 is non-fluorescent.This work demonstrates the solvent effect on assemblies, crystal structures, and fluorescent properties of two 1D Hg(II) coordination polymers with a versatile tripyridyltriazole tecton.
Co-reporter:Cheng-Peng Li, Jing Chen, Miao Du
Polyhedron 2010 29(1) pp: 463-469
Publication Date(Web):
DOI:10.1016/j.poly.2009.06.041
Co-reporter:Miao Du, Zhi-Hui Zhang, Wei Guo and Xiao-Juan Fu
Crystal Growth & Design 2009 Volume 9(Issue 4) pp:1655-1657
Publication Date(Web):March 4, 2009
DOI:10.1021/cg801393a
Assembly of pamoic acid (H2PA) with piperazine (PIPO) or 4,4′-bipyridyl (BIPY) results in two distinct supramolecular complexes [(PA)·(H2PIPO)]·3H2O (1) and [(H2PA)·(BIPY)] (2). The former displays triple-helix host arrays via charge-assisted N+−H···O− interactions with the inclusion of helical water chains, whereas the latter represents the first cocrystal of pamoic acid sustaining by the familiar carboxyl-pyridyl H-bonding synthons. Notably, the structure of 1 can be dehydrated/rehydrated with retention of crystallinity.
Co-reporter:Ming-Hua Zeng, Hua-Hong Zou, Sheng Hu, Yan-Ling Zhou, Miao Du, and Hao-Ling Sun
Crystal Growth & Design 2009 Volume 9(Issue 10) pp:4239
Publication Date(Web):August 20, 2009
DOI:10.1021/cg9005696
Two related CoII 5-aminoisophthalate coordination frameworks [Co5(μ3−OH)2(5-NH2-bdc)4(H2O)2]·7.5H2O (1, 5-NH2-bdc = 5-aminoisophthalate) and [Co5(μ3−OH)2(5-NH2-bdc)4(bpy)0.5(H2O)]·3H2O (2, bpy = 4,4′-bipyridine) based on [Co5(μ3−OH)2] clusters have been synthesized by hydrothermal reaction, structurally described, as well as properties characterized, that have unusual 3D networks with high connectivity (3,12) and (3,13)-connected, respectively. Notably, the unique (3,13)-connected framework is constructed from the (3,12)-connected network analogue and 4,4′-bipyridyl spacer. Magnetic studies show that a dominant antiferromagnetic coupling between Co(II) ions, and the generation of relatively effective noncompensated moments at very low temperature, mainly arises from the cooperative magnetic effect of the intercluster arrangement in the Td−SP-3Oh mixed-geometry-based pentamer.
Co-reporter:Miao Du, Cheng-Peng Li and Jian-Hua Guo
CrystEngComm 2009 vol. 11(Issue 8) pp:1536-1540
Publication Date(Web):26 May 2009
DOI:10.1039/B903074C
Reaction of isonicotinic acid N-oxide (HINO) with AgClO4 or AgBF4 under similar conditions unexpectedly generates two distinct crystalline products {[Ag3(INO)2(HINO)2]·(ClO4)}n (1) and {[Ag(INO)]·(H2O)}n (2). Complex 1 consists of a 3-D cationic net with mixed-connected topology and the included perchlorate counterions, whereas 2 has a 3-D neutral open framework (4-connected crb topology) with the accommodation of lattice water. The anion exchange/competition and guest desorption/adsorption behavior have also been thoroughly explored.
Co-reporter:Xiu-Juan Jiang, Su-Zhen Zhang, Jian-Hua Guo, Xiu-Guang Wang, Jin-Shan Li and Miao Du
CrystEngComm 2009 vol. 11(Issue 5) pp:855-864
Publication Date(Web):29 Jan 2009
DOI:10.1039/B818567K
A family of new coordination polymers based on a V-shaped flexible dicarboxyl building block 4,4′-(hexafluoroisopropylidene)bis(benzoic acid) and familiar metal ions (MnII, CoII, NiII, CuII, ZnII, and AgI) have been prepared and structurally characterized. Their thermal stability and solid state luminescent properties of the ZnII and AgI complexes have also been investigated. Single-crystal X-ray diffraction analysis reveals a significant structural diversity of these coordination frameworks, such as the 1-D zigzag chain, 2-fold interpenetrating layer composed of 21 helical arrays, and 3-D open network with 42 helicity and pcu topology based on the rod-shaped secondary building units (SBUs). Additionally, hydrogen bonding interactions are found in these structures to further extend or stabilize the coordination motifs. A comprehensive analysis of the coordination systems based on this dicarboxyl tecton also demonstrates that it is an excellent candidate for the design and construction of multiform metal–organic frameworks (especially helical arrays), which can be dominated by metal ions and/or synthetic conditions.
Co-reporter:Miao Du, Xiu-Juan Jiang, Xue Tan, Zhi-Hui Zhang and Hua Cai
CrystEngComm 2009 vol. 11(Issue 3) pp:454-462
Publication Date(Web):13 Oct 2008
DOI:10.1039/B811132D
Co-crystallization of a versatile building module 4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole (4-bpt) with isophthalic acid (H2ip) and its 5-substituted derivatives R–H2ip (R = –NH2, –SO3H, and –CO2H) affords a series of supramolecular solids 1–5. All compounds have been characterized by IR, microanalysis, and powder X-ray diffraction, and their thermal stability has been investigated by TG-DTA technique. Single crystal X-ray diffraction reveals that compounds 1 and 2 with the formula [(H2ip)·(4-bpt)] exhibit polymorphism, which can be isolated via a similar synthetic procedure without or with the metal ion as structure-directing reagent, and display distinct hydrogen-bonding assemblies of 3-D and double-layer networks, respectively. Multifarious 3-D supramolecular architectures are observed for compounds [(NH2–H2ip)·(4-bpt)] (3), [(SO3–H2ip)−·(H-4-bpt)+]·2H2O (4), and [(CO2H–H2ip)·(4-bpt)]·2H2O (5), in which the substituent groups of isophthalic acid are involved in different hydrogen-bonding interactions. The results clearly display the substituent effect on the structural assembly of organic co-crystals, which will be significant in the rational design and construction of such crystalline materials with specific hydrogen-bonding networks.
Co-reporter:Mei-Li Zhang, Dong-Sheng Li, Ji-Jiang Wang, Feng Fu, Miao Du, Kun Zou and Xiao-Ming Gao
Dalton Transactions 2009 (Issue 27) pp:5355-5364
Publication Date(Web):19 May 2009
DOI:10.1039/B901418G
A series of ZnII and CdII complexes with a flexible dicarboxylate building block and various heterocyclic co-ligands, formulated as {[Zn2(pda)2(phen)2]·2H2O}n (1), {[Zn(pda)(dpe)]·H2O}n (2), [Zn(pda)(bpp)]n (3), {[Cd2(pda)2(2,2′-bipy)2]·2H2O}n (4), {[Cd(pda)(4,4′-bipy)(H2O)]·H2O}n (5) and {[Cd2(pda)2(bpp)3]·14H2O}n (6) (pda = 1,3-phenylenediacetate, phen = 1,10-phenanthroline, dpe = 1,2-di(4-pyridyl)ethylene, bpp = 1,3-bi(4-pyridyl)propane, 2,2′-bipy = 2,2′-bipyridine, and 4,4′-bipy = 4,4′-bipyridine), have been synthesized and structurally characterized. In 1, the (H2O)8clusters interlink the cyclic coordination dimers to give a 3D network through hydrogen bonding. Both 2 and 3 feature 2D corrugated (4,4) layers, which are of 2-fold interpenetrating for 3. In 4, the dimeric CdII subunits are connected by the 1,3-pda ligands to generate a rampart-shaped 1D chain motif. As for 5, the [Cd(pda)]2 rings are connected by the paired 4,4′-bipy ligands to afford a tube-shaped 1D motif. In contrast to 1–5, complex 6 displays a 3D diamond network and, interestingly, the T5(0)A(0)A(2) water tapes are found to locate in the channels of this 3-D array. A structural comparison of these complexes demonstrates that the characteristics of auxiliary ligands (from chelating to bridging) play a key role in governing the coordination motifs as well as the 3-D supramolecular lattices. Solid-state properties such as photoluminescence and thermal stability of 1–6 have also been studied.
Co-reporter:Sheng-Chun Chen, Zhi-Hui Zhang, Qun Chen, Hai-Bo Gao, Qi Liu, Ming-Yang He, Miao Du
Inorganic Chemistry Communications 2009 Volume 12(Issue 9) pp:835-838
Publication Date(Web):September 2009
DOI:10.1016/j.inoche.2009.06.029
Two three-dimensional (3-D) PbII coordination frameworks [Pb(BDC-F4)(CH3OH)]n (1) and [Pb(BDC-F4)(DMF)(CH3OH)]n (2) have been prepared by the reactions of Pb(NO3)2 with a rigid dicarboxyl compound tetrafluoroterephthalic acid (H2BDC-F4) in different solvents. Single crystal X-ray diffraction reveals that both complexes show the unusual rod-based coordination networks with sra topology, although they crystallize in different space groups (C2/c and P1¯). Their spectroscopic, thermal, and fluorescence properties have also been studied.This work presents two novel 3-D lead(II) coordination frameworks with tetrafluoroterephthalate, exhibiting sra type network structures based on infinite rod-shaped building units.
Co-reporter:Miao Du, Zhi-Hui Zhang, Xiu-Guang Wang, Xiao-Jun Zhao
Inorganica Chimica Acta 2009 Volume 362(Issue 4) pp:1358-1360
Publication Date(Web):2 March 2009
DOI:10.1016/j.ica.2008.05.015
Assembly of N,N′-bis(4-picolinoyl)hydrazine (H2L) with cadmium nitrate in the presence of dicyanamide anion (dca) affords a new coordination polymer {[Cd(HL)(dca)] · (H2O)0.5}n (1), in which the [Cd(HL)]n layers are extended by dca bridges to result in a three-dimensional (3-D) coordination framework. The network structure of 1 has unusual (3,5)-connectivity and represents a new type of (4·62)(4·66·83) topology. Two such identical and complementary networks are entangled to generate a twofold parallel interpenetrating supramolecular lattice.Assembly of N,N′-bis(4-picolinoyl)hydrazine with cadmium nitrate in the presence of dicyanamide anion yields a 3-D coordination polymer, which has a unique (3,5)-connected (4·62)(4·66·83) network structure of twofold interpenetration.
Co-reporter:Su-Zhen Zhang, Zhi-Hui Zhang, Cheng-Peng Li, Miao Du
Inorganic Chemistry Communications 2009 Volume 12(Issue 10) pp:1038-1041
Publication Date(Web):October 2009
DOI:10.1016/j.inoche.2009.08.015
Co-reporter:Xiu-Juan Jiang, Miao Du, Yan Sun, Jian-Hua Guo, Jin-Shan Li
Journal of Solid State Chemistry 2009 Volume 182(Issue 11) pp:3211-3214
Publication Date(Web):November 2009
DOI:10.1016/j.jssc.2009.09.004
Reactions of different metal salts with 3-pyridin-4-yl-benzoic acid (3,4-Hpybz) under ambient condition afford a series of 3-D metal-organic frameworks with two new types of (3,6)-connected net topologies. In the isomorphic complexes [M2(μ-H2O)(3,4-pybz)4]n (MII=MnII for 1, ZnII for 2, or CdII for 3), the octahedral metal nodes are extended by the 3-connected pybz tectons to constitute 3-D arrays with the Schläfli symbol of (3.4.5)(32.44.55.62.72), whereas [Pb(3,4-pybz)2]n (4) shows a completely different 3-D (42.6)2(44.62.89) framework, which represents a subnet of the (4,8)-connected fluorite lattice.This work presents a series of 3-D metal-organic frameworks with 3-pyridin-4-yl-benzoate, which display new (3,6)-connected net topologies of (3.4.5)(32.44.55.62.72) for MnII/ZnII/CdII and (42.6)2(44.62.89) for PbII species.
Co-reporter:Qian Yu, Cheng-Peng Li, Zhi-Hui Zhang, Miao Du
Polyhedron 2009 28(12) pp: 2347-2354
Publication Date(Web):
DOI:10.1016/j.poly.2009.04.049
Co-reporter:Xu-Dong Chen Dr.;Xiao-Hu Zhao;Min Chen Dr.
Chemistry - A European Journal 2009 Volume 15( Issue 47) pp:
Publication Date(Web):
DOI:10.1002/chem.200990186
Co-reporter:Xu-Dong Chen Dr.;Xiao-Hu Zhao;Min Chen Dr.
Chemistry - A European Journal 2009 Volume 15( Issue 47) pp:12974-12977
Publication Date(Web):
DOI:10.1002/chem.200902306
Co-reporter:Xu-Dong Chen, Hui-Fang Wu and Miao Du
Chemical Communications 2008 (Issue 11) pp:1296-1298
Publication Date(Web):11 Jan 2008
DOI:10.1039/B716461K
Controlled assembly of ZnII with a versatile ligand 5-(4-pyridyl)-1H-1,2,4-triazole-3-thiol (Hptt) in conventional or solvothermal condition affords two distinct coordination frameworks, in which the former shows a unique 3-D pseudo-polyrotaxane architecture with 1-D water tapes penetrating the 2-D Zn–ptt layers, whereas the later is generated from in situ S–S coupling of Hptt and has a very rare 2-fold interpenetrating LiGe (lig) topology.
Co-reporter:Sheng-Chun Chen, Zhi-Hui Zhang, Kun-Lin Huang, Qun Chen, Ming-Yang He, Ai-Jun Cui, Chao Li, Qi Liu and Miao Du
Crystal Growth & Design 2008 Volume 8(Issue 9) pp:3437-3445
Publication Date(Web):July 23, 2008
DOI:10.1021/cg8003905
With solvent molecules participating in coordination systems, four new MnII coordination polymers of the rigid ligand 2,3,5,6-tetrachloro-1,4-benzenedicarboxylic acid (H2BDC-Cl4) have been obtained from different solvent media. Single-crystal X-ray analysis indicates that the coordination arrays of 1−4 vary from 1D fishbone or zigzag chain for 1 or 2, 2D (4,4) layer for 3, to 3D SrAl2 coordination network for 4, respectively. In {[Mn(BDC-Cl4)(py)2(H2O)2](py)2}n (1) and {[Mn(BDC-Cl4)(MeOH)3](MeOH)}n (2), pyridine/water (in 1) and MeOH (in 2) molecules act as the monodentate terminal ligands to fulfill the metal coordination spheres. In the case of {[Mn(BDC-Cl4)(dioxane)(H2O)2](dioxane)}n (3), the aqua ligand is monodentate and the dioxane moiety displays unusual bridging bidentate mode, whereas for [Mn5(BDC-Cl4)5(DMF)5]n (4), three MnII centers are connected by four BDC-Cl4 ligands and two DMF molecules to constitute a trimeric unit. These secondary units are extended to the final 3D network with SrAl2 (sra) topology. Significantly, the solvents play an essential role in the crystallization and construction of these coordination frameworks with distinct dimensionality and connectivity. The thermal and photoluminescence properties of complexes 1−4 in the solid state have also been discussed.
Co-reporter:Feng Fu, Dong-Sheng Li, Cui-Qiao Zhang, Ji-Jiang Wang, Ya-Pan Wu, Miao Du, Ji-Wu Wang
Inorganic Chemistry Communications 2008 Volume 11(Issue 10) pp:1260-1263
Publication Date(Web):October 2008
DOI:10.1016/j.inoche.2008.07.021
A novel 3D coordination polymer {[Dy2(bpdc)3(H2O)3] · H2O}n (bpdc = 2,2′-bipyridine-4,4′- dicarboxylate) based on inorganic rod-shaped infinite secondary building unit is presented, which possesses unusual mixed-connected network topology and shows high thermal stability and strong photoluminescence at room temperature.A novel coordination polymer {[Dy2(bpdc)3(H2O)3] · H2O}n has been successfully synthesized through hydrothermal route, which shows unusual mixed-connected network topology as well as high thermal stability and strong fluorescent emission.
Co-reporter:Qun Chen, Sheng-Chun Chen, Bo Xiao, Zhi-Hui Zhang, Ming-Yang He, Fang-Hua Yin, Miao Du
Inorganic Chemistry Communications 2008 Volume 11(Issue 11) pp:1371-1374
Publication Date(Web):November 2008
DOI:10.1016/j.inoche.2008.09.005
Reaction of a flexible pyridinecarboxamide ligand N,N′-[(2,3,5,6-tetrafluoro-1,4-phenylene) bis(methylene)]bis(pyridine-4-carboxamide) (H2tfpbbp) with CuII chloride or perchlorate affords two coordination polymers {[Cu(H2tfpbbp)(tfpbbp)(H2O)] · 2DMF · 4H2O}n (1) and {[Cu(H2tfpbbp)2(ClO4)2] · 3H2O}n (2). Both complexes have 2-D (4,4) layered networks extended by the exo-bidentate bridging ligands, which however consist of distinct [Cu–ligand]4 meshes owing to the conformational difference of ligands. Their spectroscopic, thermal, and fluorescence properties have also been investigated.This work presents two layered CuII coordination polymers with a flexible pyridinecarboxamide building block, and their significant structural discrepancy of the open and close 2-D networks results from the conformational isomerism of the ligands.
Co-reporter:Xiao-Jun Zhao, Zhi-Hui Zhang, Ying Wang, Miao Du
Inorganica Chimica Acta 2007 Volume 360(Issue 6) pp:1921-1928
Publication Date(Web):20 April 2007
DOI:10.1016/j.ica.2006.10.002
One-pot reactions of transition metal (CuII, NiII, CoII, or CdII) salt with malonic acid (H2mal) in the presence of mesocyclic diamine generate three supramolecular complexes and a coordination polymer. [Cu(mal)2(H2O)2](H2O)2(H2DACH) (1) and [M(mal)2(H2O)2](H2DACO) (M = Ni for 2, and Co for 3) are ion-pair products and managed by charge-assistant noncovalent interactions (DACO = 1,5-diazacyclooctane, and DACH = 1,4-diazacycloheptane). In these structures, the similar mononuclear [M(mal)2(H2O)2]2− building blocks are connected by hydrogen bonds to form 2D networks (with the aid of one lattice water in the case of 1), which are further extended by the cationic diamine components to yield 3D pillar-layered solids. While [Cd(mal)(H2O)2]n (4) is a neutral polymeric complex, in which the similar [Cd(mal)2(H2O)2]2− subunits are propagated by additional Cd–O coordinative forces to result in the final 2D layer.This work demonstrates that the mononuclear anionic [M(malonate)2(H2O)2]2− entities are reliable building blocks for the rational design of inorganic–organic hybrid crystalline materials via charge-assistant hydrogen bonding.
Co-reporter:Xiao-Jun Zhao, Qian Wang, Miao Du
Inorganica Chimica Acta 2007 Volume 360(Issue 6) pp:1970-1976
Publication Date(Web):20 April 2007
DOI:10.1016/j.ica.2006.10.011
The coordination chemistry of a flexible poly(triazolyl)alkane derivative, fluconazole (HFlu), with a series of transition metal ions and dicyanamide (dca) anionic co-ligand has been explored to afford six new metal–organic coordination polymers. Complexes [M(HFlu)2(dca)2]n (M = MnII for 1, FeII for 2, CoII for 3, ZnII for 5, and CdII for 6) have the isostructural 1-D double-chain array via bridging fluconazole, whereas [Cu3(Flu)2(dca)4(CH3OH)2]n (4) shows an unusual 2-D layered metal–organic framework with dimeric CuII subunits. Notably, both types of coordination patterns are extended into distinct 3-D supramolecular networks via hydrogen-bonding interactions. This result indicates that the choice of metal ion has a significant effect on these polymeric structures as well as the binding modes of the ligands, which is discussed in detail. The ZnII and CdII complexes 5 and 6 display similar fluorescent emissions at 260 nm in the solid state, which essentially are intraligand transitions.A series of six MnII, FeII, CoII, CuII, ZnII, and CdII coordination polymers with a flexible poly(triazolyl)alkane derivative (fluconazole) and dicyanamide co-ligand have been achieved. Single-crystal X-ray diffraction analysis suggests that these complexes display 1-D double chain or 2-D layered coordination framework, relying on the choice of metal ions.
Co-reporter:Miao Du, Cheng-Peng Li, Yan-Ping You, Xiu-Juan Jiang, Hua Cai, Qian Wang, Jian-Hua Guo
Inorganica Chimica Acta 2007 Volume 360(Issue 6) pp:2169-2174
Publication Date(Web):20 April 2007
DOI:10.1016/j.ica.2006.09.024
Assemblies of an angular dipyridyl ligand 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo) with a series of metal perchlorate afford five new supramolecular complexes with the general formula of [M(4-bpo)2(H2O)4] · (4-bpo)2 · (anion) · (solvent), in which M = MnII for 1, FeII for 2, CoII for 3, ZnII for 4, and FeIII for 5. Although similar molecular structures and compositions are found for these mononuclear complexes, they display two types of supramolecular lattices. Complexes 1, 4 and 5 similarly crystallize in space group P2/n or P2/c. The complex cations, free 4-bpo and lattice water are linked to generate 2D layered frameworks with the aid of hydrogen bonding, and the counter anions are located within and between (also methanol in 5) these 2D arrays. However, complexes 2 and 3 are isostructural in space group P1¯. Two types of alternate 2D layers consisting of complex cations and free 4-bpo components, respectively, are observed with the anions and lattice water locating between them. These motifs are interlinked by complicated hydrogen-bonding to form a 3D intercalated network. Moreover, when Co(NO3)2 is used instead of Co(ClO4)2 in the assembly of 3, a 1D polymeric chain complex {[Co(4-bpo)(H2O)2(NO3)2](H2O)3}n (6) is generated. These results indicate that the choice of metal ion and anion exerts a significant influence on governing the target complexes. A comparison of the structural features for all metal perchlorate complexes with 4-bpo is also briefly discussed.A series of mononuclear MnII, FeII, CoII, ZnII and FeIII supramolecular complexes 1–5 with a bent dipyridyl ligand 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo) have been prepared and structural characterized by X-ray diffraction. Interestingly, they display quite similar molecular structures and compositions, whereas two distinct types of supramolecular crystallizing lattices are directed by the metal ions. Anion-controlled assembly of a 1-D polymeric chain complex 6 is also described.
Co-reporter:Miao Du ;Zhi-Hui Zhang;Liang-Fu Tang ;Xiu-Guang Wang;Xiao-Jun Zhao ;Stuart R. Batten Dr.
Chemistry - A European Journal 2007 Volume 13(Issue 9) pp:
Publication Date(Web):22 DEC 2006
DOI:10.1002/chem.200600980
To systematically explore the higher-dimensional network structures with mixed connectivity, a series of two-dimensional (2D) and three-dimensional (3D) metal–organic frameworks (MOFs) with unusual (3,6)-connected net topologies are presented. These crystalline materials include [{[Mn(btza)2(H2O)2]⋅2 H2O}n] (1), [{[Zn(btza)2(H2O)2]⋅2 H2O}n] (2), [{[Cu(btza)2]⋅H2O}n] (3), and [{[Cd(btza)2]⋅3 H2O}n] (4), which have been successfully assembled through a predesigned three-connected organic component bis(1,2,4-triazol-1-yl)acetate (btza) with a variety of octahedral metal cores based on the modular synthetic methodology. The topological paradigms shown in this work cover the 2D CdCl2, 3D (42.6)2(44.62.87.102), and pyrite (pyr) types. That is, when properly treated with the familiar first-row divalent metal ions, btza may perfectly furnish the coordination spheres for effective connectivity to result in diverse (3,6)-connected nets. Beyond this, a detailed analysis of network topology for all known 3D (3,6)-connected frameworks in both inorganic and inorganic–organic hybrid materials is described. Specific network connectivity of these MOFs indicates that the metal centers represent the most significant and alterable factor in structural assembly, although they show reliable and similar geometries. In this context, the combination of the distinct d10 AgI ion with btza in different solvents affords two isomorphous MOFs [{[Ag(btza)]⋅glycol}n] (5) and [{[Ag(btza)]⋅CH3OH}n] (6) with a binodal 4-connected 3D SrAl2 (sra) topology. The network structures of MOFs 1–3 and 5 turn out to be more complicated and interesting if one considers the hydrogen bonding between the host coordination frameworks and the intercalated solvent molecules. Furthermore, the role of the included solvents in the generation and stabilization of MOFs 1–6 is also investigated.
Co-reporter:Miao Du;Xiu-Juan Jiang;Xiao-Jun Zhao;Hua Cai;Joan Ribas
European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 6) pp:
Publication Date(Web):26 JAN 2006
DOI:10.1002/ejic.200500822
Reactions of mixed ligands succinic acid (H2suc) and bent dipyridines, such as 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) and its 4-N-donor analog (4-bpo), with inorganic CuII, NiII, and CdII salts yield three new metal-organic coordination frameworks {[Cu(suc)(3-bpo)(H2O)2]·(H2O)1.75}n (1), {[Ni(suc)(4-bpo)(H2O)2]·(H2O)5}n (3), and {[Cd2(suc)2(3-bpo)2(H2O)2]·(H2O)6.75}n (4), in which the metal centers are linked by bridging ligands 3-bpo/4-bpo and suc2– along two directions to form 2D infinite networks. The corrugated 2D nets of 1 and 4, obtained under hydrothermal conditions, align in an interdigitated manner with the presence of significant aromatic-stacking interactions to result in similar 3D architectures. The 2D sheets in 3 are extended by interlayer hydrogen bonds to afford a 3D structure. However, when succinic acid is replaced by fumaric acid (H2fum) in the reaction with 3-bpo and CuII salt, a metallacyclophane [Cu(Hfum)2(3-bpo)(H2O)]2·(3-bpo)2·(H2O)6 (2) is generated. The binuclear coordinated motifs are hydrogen-bonded to the lattice water chains to furnish a unique 3D channel-like framework, in which the guest 3-bpo molecules are accommodated. The thermal stabilities of these new materials were investigated by thermogravimetric analysis (TGA) of mass loss. The magnetic coupling in complexes 1–3 is antiferromagnetic and very small, which is as expected considering the long organic bridges between the paramagnetic centers. The solid-state luminescence properties of 4 reveal an intense fluorescence emission at 378 nm. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Co-reporter:Miao Du, Hua Cai, Xiao-Jun Zhao
Inorganica Chimica Acta 2006 Volume 359(Issue 2) pp:673-679
Publication Date(Web):20 January 2006
DOI:10.1016/j.ica.2005.08.004
Reaction of M(OAc)2 (MII = CuII for 1, CoII for 2, and PbII for 3) with pyridine-2,6-dicarboxylic acid (H2pydc) in presence of a dipyridyl spacer 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (bpo) affords three novel metal-organic supramolecular networks [Cu2(bpo)(pydc)2(H2O)3] · 2.75H2O(1), [Co(bpo)(pydc)(H2O)2] · (H2O) (2) and [Pb(pydc)]n (3), which have been structurally determined by single-crystal X-ray diffraction. The dimeric Cu-pydc coordination framework bridged by a bpo spacer in 1 is hydrogen-bonded to four others to result in a two-dimensional (2-D) sheet array. The neutral monomeric molecules in 2 have an ordered 3-D stacking stabilized via hydrogen bonds and significant π–π interactions in the lattice, possessing large porous channels with the inclusion of guest solvates. In coordination polymer 3, the PbII ion takes the unusual distorted capped trigonal prismatic geometry (PbNO6) and each pydc dianion binds to four PbII centres to form a 2-D infinite network. The thermal stabilities of these complexes have also been investigated.Three new metal pyridine-2,6-dicarboxylate (pydc) supramolecular networks [Cu2(bpo)(pydc)2(H2O)3] · 2.75H2O (1), [Co(bpo)(pydc)(H2O)2] · (H2O) (2) and [Pb(pydc)]n (3), were hydrothermally prepared in presence of a bent dipyridyl spacer 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (bpo). The bpo-bridged dinuclear complex 1 exhibits a 2-D hydrogen-bonded sheet and the coordination polymer 3 has a 2-D infinite metal-organic framework. Significantly, the monomeric complex 2 display a unique 3-D supramolecular architecture with large porous channels formed through hydrogen-bonding and aromatic stacking interactions.
Co-reporter:Miao Du, Qian Wang, Ying Wang, Xiao-Jun Zhao, Joan Ribas
Journal of Solid State Chemistry 2006 Volume 179(Issue 12) pp:3926-3936
Publication Date(Web):December 2006
DOI:10.1016/j.jssc.2006.08.039
A series of metal dicyanamide (dca) coordination polymers combined with cyanopyridine (cypy) terminal co-ligands, namely, [Co2(dca)4(4-cypy)4]n (1), [Cd(dca)2(4-cypy)2]n (2), [Fe(dca)2(3-cypy)2]n (3) and [Co(dca)2(3-cypy)2]n (4), have been synthesized at the ambient conditions. X-ray single crystal diffraction reveals that complexes 1–4 have similar metal-dca coordination layers in which the octahedral metal centers are connected by μ1,5-dca linkers. Notably, three types of 3-D packing lattices are observed for these layered arrays. The thermal stabilities of such new crystalline materials have been studied by thermogravimetric analysis of mass loss. The magnetic properties of the CoII and FeII complexes have been investigated and discussed in detail. A discrete mononuclear molecule [Cd(dca)2(pyom)2] (5) is also described, in which the chelated ligand O-methyl picolinimidate (pyom) arises from the addition of methanol solvent across the CN bond of 2-cypy.A series of new metal dicyanamide complexes with cyanopyridine terminal co-ligands have been prepared and structurally determined by X-ray single-crystal diffraction. The magnetic properties of the CoII and FeII layered coordination polymers are also discussed.
Co-reporter:Miao Du, Cheng-Peng Li, Jian-Hua Guo
Inorganica Chimica Acta 2006 Volume 359(Issue 8) pp:2575-2582
Publication Date(Web):15 May 2006
DOI:10.1016/j.ica.2006.02.039
The reactions of 2,5-bis(pyrazinyl)-1,3,4-oxadiazole (bpzo) with CdII or CoII salt in the presence of thiocyanate afford two distinct complexes, a 1-D coordination array [Cd(bpzo)2(SCN)2]n (1) and a 3-D hydrogen-bonded supramolecular network [Co(bpzo)2(SCN)2(H2O)2](CH3CN)2(H2O)2 (2). X-ray single-crystal structural determination reveals that the extended networks of complexes 1 and 2 are manipulated via different directional propagating forces. In 1, the adjacent CdII centers are bridged by a pair of μ1,3-SCN− anions to form a 1-D array, whereas in 2, the monomeric CoII coordination entities are hydrogen-bonded into a novel 3-D architecture in which the thiocyanate ions take the only N-binding mode. In both cases, bpzo behaves as monodentate terminals. These results indicate that the choice of metal ions does play a critical role in the supramolecular assembly. The structural and binding features of bpzo in all related compounds have also been discussed.Assemblies of CdII or CoII thiocyanate with a multidentate organic ligand 2,5-bis(pyrazinyl)-1,3,4-oxadiazole (bpzo) generate a 1-D coordinated chain [Cd(bpzo)2(SCN)2]n (1) and a monomeric complex [Co(bpzo)2(SCN)2(H2O)2](CH3CN)2(H2O)2 (2). In both structures, bpzo is monodentate coordination, whereas the thiocyanate ions take the bridging or terminal modes, respectively. The neutral CoII complex units and lattice water molecules in 2 are interlinked to result in a novel 3-D hydrogen-bonded network with 1-D channels, in which the acetonitrile guests are included. This work reveals that the metal ions do play a critical role in tuning the network structures.
Co-reporter:Miao Du, Cheng-Peng Li
Inorganica Chimica Acta 2006 Volume 359(Issue 5) pp:1690-1696
Publication Date(Web):20 March 2006
DOI:10.1016/j.ica.2005.11.038
Self-assemblies of 4-pyridylthioacetic acid (Hpyta) with CdCl2 or HgCl2 yield the polymeric metal-organic coordination frameworks [Cd(pyta)2(H2O)]n (1) and [Hg(pyta)Cl]n (2). X-ray single-crystal diffraction results reveal that both complexes display similar 1-D neutral coordination arrays containing approximate rectangular molecular box subunits, which are, however, linked via mononuclear CdII and dinuclear Hg2O2 nodes. For 1, the adjacent 1-D motifs are interconnected to form a 2-D layer via O–H⋯O hydrogen bonds and further engender a 3-D network by weak S⋯S interactions; whereas complex 2 possesses a novel 3-D supramolecular architecture with the aid of abundant C–H⋯Cl and S⋯S contacts. Interestingly, due to the intrinsic difference of the metal ions, the carboxylate group of the pyta ligand displays symmetric bidentate chelate mode for 1 and monoatomic bridging fashion for 2; the latter case is unprecedented in coordination chemistry of pyta. These results clearly suggest that it is an effective synthetic strategy by employing coordinative forces and concomitant noncovalent contacts to construct the fine-tuning supramolecular networks.Two 1-D molecular-box based coordination polymers [Cd(pyta)2(H2O)]n (1) and [Hg(pyta)Cl]n (2) with different mono- and di-nuclear nodes directed by the metal ion selection, are achieved by assembly of metal chloride with a versatile flexible molecule 4-pyridylthioacetic acid (Hpyta). The 3-D supramolecular architectures for both complexes with the aid of hydrogen-bonding and weak S⋯S interactions are further analyzed, suggesting that such noncovalent contacts are also important elements in tuning the network structures. The binding features of pyta in all known complexes have been discussed in detail.
Co-reporter:Miao Du, Xiu-Juan Jiang and Xiao-Jun Zhao
Chemical Communications 2005 (Issue 44) pp:5521-5523
Publication Date(Web):07 Oct 2005
DOI:10.1039/B509875K
The reaction of CuII or CdII acetate with mixed ligands terephthalic (tp) and 3,5-bis(4-pyridyl)-4-amino-1,2,4-triazole (bpt) under the same conditions affords two unusual metal–organic frameworks, in which 1 represents a new type of polythreaded supramolecular architecture consisting of distinct 1-D and 2-D coordination polymers within one crystal, however, 2 has an interpenetrating porous network with two similar laterally interlocking 2-D (4,4) layers.
Co-reporter:Miao Du, Xiao-Jun Zhao, Jian-Hua Guo and Stuart R. Batten
Chemical Communications 2005 (Issue 38) pp:4836-4838
Publication Date(Web):02 Sep 2005
DOI:10.1039/B508479B
The construction of two types of coordination polymers with closely related 4-connected topologies [PtS and lvt (42.84)] were achieved based on a well-designed bent dipyrazine linker, and the topological differences only result from the stereochemistry of silver(I) coordination sphere with the same coordination donors. Selective anion-exchange functions of the series of PtS-type coordination networks containing different counter anions (from small BF4− to very large SbF6−) were identified.
Co-reporter:Miao Du;Xiao-Jun Zhao;Jian-Hua Guo;Xian-He Bu;Joan Ribas
European Journal of Inorganic Chemistry 2005 Volume 2005(Issue 2) pp:
Publication Date(Web):24 NOV 2004
DOI:10.1002/ejic.200400618
The formation of two novel phenoxo-bridged linear trimetallic CuII and NiII complexes, [Cu3(μ-L)2](CH3OH)2(ClO4)2 (1) and [Ni3(μ-L)2(CH3OH)2](ClO4)2 (2), with a new diazamesocyclic ligand functionalised by additional phenol donor pendants (H2L = N,N′- bis(2-hydroxybenzyl)-1,4-diazacycloheptane), has been achieved and both complexes have been characterised by IR spectroscopy, elemental analyses, conductivity measurements, thermal analyses and UV/Vis techniques. Single-crystal X-ray diffraction analyses revealed that both 1 and 2 have the similar phenoxo-bridged linear trinuclear cores. For 1, two terminal and the central CuII ion are in square-planar environments with the adjacent intramolecular Cu···Cu separation of 2.9376(9) Å. For 2, however, two terminal NiII ions are in square-planar environments and the central NiII ion assumes an octahedral geometry by axial coordination of two methanol ligands, the adjacent intramolecular Ni···Ni distance being 3.007(3) Å. In both cases, the 1,4-diazacycloheptane (DACH) ring adopts the normal boat configuration. The magnetic properties of complexes 1 and 2 have been investigated by variable-temperature magnetic susceptibility measurements in the solid state. Complex 1 displays a very strong antiferromagnetic coupling interaction between the neighbouring μ-phenoxo CuII centres with a J parameter of −314 cm−1 and the magneto-structural correlation for such complexes is discussed in detail. For complex 2, the result indicates that both terminal NiII ions are diamagnetic and the central NiII shows typical paramagnetic behaviour. The presence of zero-field splitting for NiII with a D parameter of 11 cm−1, being active at low temperature, is further corroborated by the magnetisation measurement at 2 K. Additionally, the interesting ESR spectra of 1 at different temperatures (from 298 K to 8 K) were investigated and interpreted. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
Co-reporter:Miao Du;Xiao-Jun Zhao
Applied Organometallic Chemistry 2005 Volume 19(Issue 1) pp:
Publication Date(Web):6 JAN 2005
DOI:10.1002/aoc.782
The centrosymmetric {[(HOOCCH2PPh2)]2(CH2)4}2+ cation adopts an extended conformation in which the phosphorus center adopts a tetrahedral geometry. OH···O and CH···O hydrogen bonding interactions expand this structure to form a two-dimensional layered architecture. Copyright © 2005 John Wiley & Sons, Ltd.
Co-reporter:Miao Du, Hua Cai, Xiao-Jun Zhao
Inorganica Chimica Acta 2005 Volume 358(Issue 13) pp:4034-4038
Publication Date(Web):1 September 2005
DOI:10.1016/j.ica.2005.07.006
Two novel metal–organic hybrid coordination polymers {[Cu(bpo)(chdc)(H2O)](H2O)0.5}n (1) and [Pb(chdc)(H2O)]n (2) have been synthesized under different conditions and structurally characterized by single-crystal X-ray diffraction technique, where H2chdc refers to a flexible 1,4-cyclohexanedicarboxylic acid ligand and bpo is 2,5-bis(4-pyridyl)-1,3,4-oxadiazole. Complex 1 has a two-dimensional (2-D) grid-like [11.28 × 13.63 Å2] framework in which the CuII centers are extended via bidentate bridging ligands bpo and e,e-trans-chdc along two directions, exhibiting large porous cavities. Coordination polymer 2 represents the first PbII complex of H2chdc in which the larger PbII centers are connected by e,a-cis-chdc anions to afford a 2-D close-knit structure.The preparation and crystal structures of two new coordination polymers based on a flexible 1,4-cyclohexanedicarboxylic acid (H2chdc) ligand, including a 2-D grid-like network {[Cu(bpo)(chdc)(H2O)](H2O)0.5}n (1) with large porous cavities and a 2-D close-knit framework [Pb(chdc)(H2O)]n (2), representing the first PbII complex of H2chdc, are described. The differences between the conformation and coordination fashions of chdc in two cases may be due to the distinct nature of the metal centers.
Co-reporter:Miao Du, Xiao-Jun Zhao and Ying Wang
Dalton Transactions 2004 (Issue 14) pp:2065-2072
Publication Date(Web):14 Jun 2004
DOI:10.1039/B403498H
Six novel inorganic–organic coordination supramolecular networks based on a versatile linking unit 4-pyridylthioacetate (pyta) and inorganic CoII, CuII, AgI, ZnII, MnII and PbII salts have been prepared in water medium and structurally characterized by single-crystal X-ray diffraction analysis. Reaction of CoCl2·6H2O with Hpyta afforded a neutral mononuclear complex [Co(pyta)2(H2O)4]
(1), which exhibits a two-dimensional (2-D) layered architecture through intermolecular O–H⋯O interactions. Reaction of CuCl2·2H2O with Hpyta yielded a neutral one-dimensional (1-D) coordination polymer {[Cu(pyta)2(H2O)]·0.5H2O}n
(2) consisting of rectangle molecular square units, which show a three-dimensional (3-D) supramolecular network through S⋯S and O–H⋯O weak interactions. However, when AgNO3, Zn(OAc)2·2H2O or MnCl2·4H2O salts were used in the above self-assembled processes, the neutral 2-D coordination polymers [Ag(pyta)]n
(3), {[Zn(pyta)2]·4H2O}n
(4) or {[Mn(pyta)2(H2O)]}n
(5) with different topologies were obtained, respectively. While substituting the transition metal ions used in 1–5 with Pb(OAc)2·3H2O, a one-dimensional coordination polymer [Pb(pyta)2]n
(6), which shows a novel 2-fold interpenetrating 2-D supramolecular architecture through weak S⋯S interactions, was isolated. It is interesting to note that the building block pyta anion exhibits different configurations and coordination modes in the solid structures of complexes 1–6. These results indicate that the versatile nature of this flexible ligand, together with the coordination preferences of the metal centers, play a critical role in construction of these novel coordination polymers or supramolecules. The spectral and thermal properties of these new materials have also been investigated.
Co-reporter:Miao Du;Xiao-Jun Zhao
Applied Organometallic Chemistry 2004 Volume 18(Issue 9) pp:
Publication Date(Web):19 AUG 2004
DOI:10.1002/aoc.713
The centrosymmetric cation {[(HOOCCH2PPh2)]2(CH2)4}2+ adopts an extended conformation. The phosphorus atom shows a tetrahedral coordination and each OH of the carboxylic group is hydrogen bonded to a bromide ion. Copyright © 2004 John Wiley & Sons, Ltd.
Co-reporter:Miao Du;Xiao-Jun Zhao
Applied Organometallic Chemistry 2004 Volume 18(Issue 2) pp:
Publication Date(Web):28 JAN 2004
DOI:10.1002/aoc.576
In mononuclear [Zn(C10H9N3)2(N3)2]·H2O, the zinc atom has an approximate octahedral geometry, coordinated with four pyridyl nitrogen atoms derived from two bis(2-pyridyl)amine molecules and two terminal nitrogen donors of the azide anions. Hydrogen-bonding interactions extend this structure to form a double-layer architecture. Copyright © 2004 John Wiley & Sons, Ltd.
Co-reporter:Shao-Ming Fang, Min Hu, Qiang Zhang, Miao Du and Chun-Sen Liu
Dalton Transactions 2011 - vol. 40(Issue 17) pp:NaN4541-4541
Publication Date(Web):2011/03/24
DOI:10.1039/C0DT00903B
A series of six Ag(I) and Zn(II) coordination polymers, namely, [Ag2(ndc)]∞ (1), {[Zn(ndc)(H2O)](H2O)}∞ (2), {[Ag2(ndc)(4bpy)2][Ag(4bpy)(H2O)](ClO4)(H2O)2}∞ (3), [Zn5(ndc)4(4bpy)2(μ3-OH)2]∞ (4), {[Ag(ndc)(abp)][Ag(abp)](H2O)3}∞ (5), and {[Zn2(ndc)2(abp)(H2O)2](H2O)2}∞ (6), have been prepared by using 2,3-naphthalenedicarboxylic acid (H2ndc), an analogue of 1,2-benzenedicarboxylic acid (H2bdc), and different 4,4′-bipyridyl-like bridging co-ligands 4,4′-bipyridine (4bpy) and trans-4,4′-azobis(pyridine) (abp). The initial complexes 1 and 2 display the unusual two-dimensional (2-D) five-connected (48.62) and the 2-D three-connected (4.82) coordination networks, respectively. When two comparable rod-like linkers 4bpy and abp (with different N,N′-donor separations of the molecular backbones of ca. 7 and 9 Å) are further introduced, two one-dimensional (1-D) complexes 3 and 5, a three-dimensional (3-D) coordination framework 4 with (43)(43.63)(43.65.82)(44.64.82)(410.65) topology and a 2-D 63 layered coordination polymer 6 are constructed. A structural comparison of these complexes with those based on the structurally related bdc ligand suggests that the extended π-conjugated system of ndc with different electronic nature and steric bulk play an important role in constructing the supramolecular architectures for 1–6, which are also regulated by different bridging N-donor co-ligands and metal ions. Moreover, complexes 1–6 show strong solid-state luminescence emissions at room temperature that mainly originate from the intraligand transitions of ndc.
Co-reporter:Miao Du, Min Chen, Xiao-Gang Yang, Jiong Wen, Xi Wang, Shao-Ming Fang and Chun-Sen Liu
Journal of Materials Chemistry A 2014 - vol. 2(Issue 25) pp:NaN9834-9834
Publication Date(Web):2014/04/15
DOI:10.1039/C4TA00963K
Stability is a critical issue in practical applications of metal–organic frameworks (MOFs). These materials are usually destroyed by heating or exposure to chemicals, which cause them to reduce or even lose their porous nature. We report here a mesoporous 437-MOF material with perfect 1-D hexagonal channels of ca. 3 nm pore size, which shows both high thermal and chemical stability. The gas sorption capacity of desolvated 437-MOF can be improved by activating the material at higher temperatures. Remarkably, optimum porosity is achieved using a combined approach of heating the sample in boiling water followed by further heating. This unexpected observation can be ascribed to the synergistic effects of the external and internal surfaces of the porous crystalline material. An exploration of the possible applications of this material in supercapacitors shows a great potential for activated 437-MOF to be used as an electrode material as a result of its high surface area (ca. 2400 m2 g−1), hierarchical pore structure, and the pseudocapacitor contribution provided by doping with In.
Co-reporter:Cheng-Peng Li, Hang Zhou, Si Wang, Hong-Han Yuan, Su-Zhen Zhang and Miao Du
Chemical Communications 2017 - vol. 53(Issue 35) pp:NaN4770-4770
Publication Date(Web):2017/04/05
DOI:10.1039/C7CC02005H
A cationic Ag(I) coordination polymer with 1D nanoporous channels (ca. 1.22 nm diameter) shows the selective and complete removal of carcinogenic dye Acid Red 26 from aqueous solution upon the size-exclusion and charge-matching effect.
Co-reporter:Cheng-Peng Li, Si Wang, Wei Guo, Yan Yan and Miao Du
Chemical Communications 2016 - vol. 52(Issue 74) pp:NaN11063-11063
Publication Date(Web):2016/08/08
DOI:10.1039/C6CC05938D
A 3-fold interpenetrated Ag(I) coordination framework can exhibit dual structure evolution behaviours driven by distinct anion-exchange courses in which irreversible single-crystal to single-crystal transformation occurs, resulting in a switching of network interpenetration degree (from 3-fold to 2-fold).
Co-reporter:Sheng-Chun Chen, Zhi-Hui Zhang, Qun Chen, Li-Qun Wang, Juan Xu, Ming-Yang He, Miao Du, Xiao-Ping Yang and Richard A. Jones
Chemical Communications 2013 - vol. 49(Issue 13) pp:NaN1272-1272
Publication Date(Web):2012/12/07
DOI:10.1039/C2CC36538C
Three isomeric water-soluble and light-stable silver(I) coordination polymers with a fluorinated carboxylate ligand were prepared by template-controlled method, which show different 2D polymeric coordination structures with a novel layered inorganic connectivity in the solid state. In water solution, they dissociate into several stable polynuclear silver(I) oligomers and exhibit extraordinary antimicrobial activities against selected bacteria.
Co-reporter:Cheng-Peng Li and Miao Du
Chemical Communications 2011 - vol. 47(Issue 21) pp:NaN5972-5972
Publication Date(Web):2011/04/08
DOI:10.1039/C1CC10935A
Solvent effect is a vital subject in the domain of coordination chemistry. In this connection, previous researches mainly focus on the role of solvents in reaction kinetics and thermodynamics during the coordination processes. In virtue of the recent efforts on coordination supramolecular systems, especially coordination polymers or metal–organic frameworks, this feature article aims to demonstrate the solvent effect on regulating such diversiform metallosupramolecular solids, incorporating their crystal growth/assembly, structural modulation, dynamic transformations, and potential applications, which may provide new insights into the rational design and construction of such advanced crystalline materials.
Co-reporter:Miao Du, Cheng-Peng Li, Jing-Min Wu, Jian-Hua Guo and Gui-Chang Wang
Chemical Communications 2011 - vol. 47(Issue 28) pp:NaN8090-8090
Publication Date(Web):2011/06/17
DOI:10.1039/C1CC12184G
This work first demonstrates that the robust [Cu2(OOCR)4] unit can be destroyed and reconstructed in the solid state, as observed in water-induced structural interconversion of two distinct coordination polymers with 5-bromonicotinate.
Co-reporter:Zhi-Hui Zhang, Sheng-Chun Chen, Jin-Ling Mi, Ming-Yang He, Qun Chen and Miao Du
Chemical Communications 2010 - vol. 46(Issue 44) pp:NaN8429-8429
Publication Date(Web):2010/10/11
DOI:10.1039/C0CC03173A
Entangled nets in coordination compounds with both self-penetrating and interpenetrating structural features have been first constructed by using a flexible bis-pyridinecarboxamide and isophthalate or 5-methylisophthalate. Distinct entangled systems showing both 3-fold interpenetration and polyrotaxane can also be obtained by altering the 5-substituents of isophthalate.
Co-reporter:Lu-Fang Ma, Jun-Wei Zhao, Min-Le Han, Li-Ya Wang and Miao Du
Dalton Transactions 2012 - vol. 41(Issue 7) pp:NaN2083-2083
Publication Date(Web):2011/12/21
DOI:10.1039/C1DT11206F
Two novel 3-D coordination polymers with different Cu(II) subunits as nodes and mixed bridging ligands as linkers, namely [Cu5(μ3-OH)2(1,3-bip)2(CH3O-ip)4]n (1) and {[Cu4(1,3-btp)2(CH3O-p)4(H2O)2]·2H2O}n (2) (CH3O-H2ip = 5-methoxyisophthalate, 1,3-bip = 1,3-bis(imidazol)propane, 1,3-btp = 1,3-bis(1,2,4-triazol-1-yl)propane), were prepared under hydrothermal conditions. Complex 1 exhibits a CsCl-type network with [Cu5(μ3-OH)2]8+ clusters acting as nodes, which represents the first 3-D network based on pentanuclear Cu(II) clusters. Complex 2 features a 3-D pillared-layer network with (4,6)-connected (44.62)(44.68.83)-fsc topology, which is a rare example of homometallic coordination polymers constructed by alternate binuclear metal clusters and single metal centres. Variable-temperature magnetic susceptibility measurements show dominant ferromagnetic interactions in the pentanuclear clusters of 1 and strong antiferromagnetic interactions in the dinuclear paddle-wheel units of 2.
Co-reporter:Chun-Sen Liu, Miao Du, E. Carolina Sañudo, Jorge Echeverria, Min Hu, Qiang Zhang, Li-Ming Zhou and Shao-Ming Fang
Dalton Transactions 2011 - vol. 40(Issue 37) pp:NaN9369-9369
Publication Date(Web):2011/08/17
DOI:10.1039/C1DT11039J
A luminescent trinuclear DyIII complex, in which the three DyIII centers with different geometries take a nearly linear disposition, shows the slow magnetic relaxation processes of single ion origin.
Co-reporter:Mei-Li Zhang, Dong-Sheng Li, Ji-Jiang Wang, Feng Fu, Miao Du, Kun Zou and Xiao-Ming Gao
Dalton Transactions 2009(Issue 27) pp:NaN5364-5364
Publication Date(Web):2009/05/19
DOI:10.1039/B901418G
A series of ZnII and CdII complexes with a flexible dicarboxylate building block and various heterocyclic co-ligands, formulated as {[Zn2(pda)2(phen)2]·2H2O}n (1), {[Zn(pda)(dpe)]·H2O}n (2), [Zn(pda)(bpp)]n (3), {[Cd2(pda)2(2,2′-bipy)2]·2H2O}n (4), {[Cd(pda)(4,4′-bipy)(H2O)]·H2O}n (5) and {[Cd2(pda)2(bpp)3]·14H2O}n (6) (pda = 1,3-phenylenediacetate, phen = 1,10-phenanthroline, dpe = 1,2-di(4-pyridyl)ethylene, bpp = 1,3-bi(4-pyridyl)propane, 2,2′-bipy = 2,2′-bipyridine, and 4,4′-bipy = 4,4′-bipyridine), have been synthesized and structurally characterized. In 1, the (H2O)8clusters interlink the cyclic coordination dimers to give a 3D network through hydrogen bonding. Both 2 and 3 feature 2D corrugated (4,4) layers, which are of 2-fold interpenetrating for 3. In 4, the dimeric CdII subunits are connected by the 1,3-pda ligands to generate a rampart-shaped 1D chain motif. As for 5, the [Cd(pda)]2 rings are connected by the paired 4,4′-bipy ligands to afford a tube-shaped 1D motif. In contrast to 1–5, complex 6 displays a 3D diamond network and, interestingly, the T5(0)A(0)A(2) water tapes are found to locate in the channels of this 3-D array. A structural comparison of these complexes demonstrates that the characteristics of auxiliary ligands (from chelating to bridging) play a key role in governing the coordination motifs as well as the 3-D supramolecular lattices. Solid-state properties such as photoluminescence and thermal stability of 1–6 have also been studied.
Co-reporter:Dong-Sheng Li, Feng Fu, Jun Zhao, Ya-Pan Wu, Miao Du, Kun Zou, Wen-Wen Dong and Yao-Yu Wang
Dalton Transactions 2010 - vol. 39(Issue 48) pp:NaN11525-11525
Publication Date(Web):2010/11/09
DOI:10.1039/C0DT00900H
Two unique six-connected self-penetrating coordination polymers with a new (44.610.8) network topology, derived from the cross-linking of two 66-dia subnets, were constructed from NiII or CoII and two types of V-shaped tectons. The NiII complex 1 shows an antiferromagnetic coupling via μ-carboxylate and μ-H2O pathways, whereas the CoII complex 2 exhibits the single-ion behavior in 300–34 K and then a ferromagnetic coupling at lower temperatures.
Co-reporter:Lu-Fang Ma, Bin Liu, Li-Ya Wang, Cheng-Peng Li and Miao Du
Dalton Transactions 2010 - vol. 39(Issue 9) pp:NaN2308-2308
Publication Date(Web):2010/01/12
DOI:10.1039/B920308G
Hydrothermal reactions of mixed ligands 5-methoxyisophthalate (CH3O-H2ip) and dipyridyl with Cu(OAc)2·2H2O afford five new coordination polymers, including {[Cu(CH3O-ip)(bpa)]·H2O}n (1), [Cu2(CH3O-ip)2(bpa)0.5(H2O)]n (2), [Cu2(CH3O-ip)2(bpp)(H2O)]n (3), {[Cu3(CH3O-ip)3(bpp)2(H2O)]·3H2O}n (4) and [Cu4(CH3O-ip)3(bpe)(OH)2]n (5) (bpp = 1,3-di(4-pyridyl)propane, bpa = 1,2-bi(4-pyridyl)ethane, and bpe = 1,2-di(4-pyridyl)ethylene). Compound 1 consists of CH3O-ip anion-bridged 1D CuII chains that are linked by trans-bpa into a 2D layer. Compound 2 is a 2D (4,4) layer that is connected by CH3O-ip anions. The gauche bpa in 2 lies in the cavity and meets the coordination requirement of the paddle-wheel dimeric copper unit. Compound 3 is an extended 3D polythreading network consisting of 2D (4,4) motifs with dangling bpp lateral arms. Compound 4 exhibits a 3D (4,6)-connected self-penetrating (65.8)(614.8) network that is composed of binuclear and mononuclear metal nodes. Compound 5 exhibits a 3D network with the tetranuclear [Cu4(μ3-OH)2]6+ cluster acting as nodes, which is constructed by the interconnection of 2D helical layers via bpe pillars. The results of magnetic determination show that the syn–anti carboxylato bridges in our cases induce a weak antiferromagnetic interaction in 1, and the syn–syn carboxylato bridge in 3 and 4 mediates a strong antiferromagnetic interaction.
Co-reporter:Cheng-Peng Li, Jing Chen, Yu-Hai Mu and Miao Du
Dalton Transactions 2015 - vol. 44(Issue 24) pp:NaN11118-11118
Publication Date(Web):2015/05/05
DOI:10.1039/C5DT00420A
Seven Zn(II) coordination complexes with 5-halonicotinic acids (HL-X, X = F, Cl, or Br) have been synthesized with different synthetic approaches, including layer diffusion or stirring method in an ambient environment and solvothermal synthesis at 100 °C. Assembly of HL-F with Zn(II) under different conditions will yield the same 2D network of [Zn(L-F)2]n (1). Interestingly, three distinct complexes, a 3D framework {[Zn2(L-Cl)4(H2O)](H2O)6}n (2) and two 2D pseudo-polymorphic isomers {[Zn(L-Cl)2](H2O)1.5}n (3) and {[Zn2(L-Cl)4](H2O)}n (4) can be obtained by reacting HL-Cl with Zn(II) under layer diffusion, stirring, and solvothermal conditions, respectively. Furthermore, replacing the –Cl substituent with –Br on the HL-X ligand will also afford three diverse coordination assemblies of 3D {[Zn2(L-Br)4(H2O)](CH3OH)2.5}n (5), mononuclear [Zn(HL-Br)2(H2O)4][L-Br]2 (6), and 2D {[Zn(L-Br)2](H2O)1.15}n (7) depending on the synthetic pathways. Beyond the significant influence of the synthetic approach, which will lead to the formation of various crystalline products, the halogen substitution effect of HL-X ligands on the coordination motifs has also been demonstrated. In addition, thermal stability and fluorescence for these crystalline materials will be presented.
Co-reporter:Xu-Dong Chen, Hui-Fang Wu and Miao Du
Chemical Communications 2008(Issue 11) pp:
Publication Date(Web):
DOI:10.1039/B716461K
Co-reporter:Chun-Sen Liu, Xiao-Gang Yang, Min Hu, Miao Du and Shao-Ming Fang
Chemical Communications 2012 - vol. 48(Issue 60) pp:NaN7461-7461
Publication Date(Web):2012/06/08
DOI:10.1039/C2CC31905E
A 3-D metal–organic framework constructed from the linear trimetallic [Cd2NaO6(H2O)6] secondary building units (SBUs) and a long flexible 6,6’-dithiodinicotinate tecton is presented, which has a 6-connected (46.69)-hxg network with high-symmetry hexagonal geometries.
Co-reporter:Min Chen, Hui Zhao, Chun-Sen Liu, Xi Wang, Heng-Zhen Shi and Miao Du
Chemical Communications 2015 - vol. 51(Issue 27) pp:NaN6017-6017
Publication Date(Web):2015/02/25
DOI:10.1039/C5CC00018A
A pair of supramolecular isomers of Co(II)-based metal–organic frameworks can be directionally constructed in virtue of solvent templates, which show diverse bilayer networks and lattice packing with the same Co3 SBUs and organic linkers. The two porous materials show distinct gas sorption behaviors at different temperatures, especially their CO2 sorption selectivity.
Co-reporter:Cheng-Peng Li, Jing Chen, Chun-Sen Liu and Miao Du
Chemical Communications 2015 - vol. 51(Issue 14) pp:NaN2781-2781
Publication Date(Web):2014/10/21
DOI:10.1039/C4CC06263A
Reactions in the solid state, especially single-crystal-to-single-crystal (SC–SC) transformations, provide an appealing pathway to obtain target crystalline materials with modified properties via a solvent-free green chemistry approach. This feature article focuses on the progress to date in the context of coordination supramolecular systems (CSSs), especially coordination polymers (CPs) or metal–organic frameworks (MOFs), which show interesting dynamic natures upon exposure to various exogenous stimuli, including concentration, temperature, light and mechanical force, as well as their synergic effect. In essence, dynamic CSSs normally possess crucial crystalline-reactive characteristics: (i) metal ions or clusters with unstable or metastable electronic configurations and coordination geometries; (ii) organic ligands bearing physicochemically active functional groups for subsequent reactions; (iii) polymeric networks of high flexibility for structural bending, rotation, swelling, or shrinking; (iv) guest moieties to be freely exchanged or eliminated by varying the environmental conditions. The significant changes in catalytic, sorption, magnetic, or luminescent properties accompanied by the structural transformations will also be discussed, which reveal the proof-of-concept thereof in designing new functional crystalline materials.
Co-reporter:Di-Ming Chen, Jia-Yue Tian, Chun-Sen Liu and Miao Du
Chemical Communications 2016 - vol. 52(Issue 54) pp:NaN8416-8416
Publication Date(Web):2016/05/24
DOI:10.1039/C6CC02359B
Incorporating the in situ formed size-matching molecular building blocks (MBBs) into the open channels will remarkably improve the robustness and gas sorption performance of an evacuated metal–organic framework. As a result, such MBBs can transfer the open metal sites from the framework walls to the channel centers and separate the large channels into multiple smaller voids, leading to a molecular sieving effect and high-performance gas-separation of the modified material.
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