Co-reporter:Run-Ping Ye;Xin Zhang;Ye-Yan Qin
CrystEngComm (1999-Present) 2017 vol. 19(Issue 12) pp:1658-1668
Publication Date(Web):2017/03/20
DOI:10.1039/C7CE00004A
Five novel interesting Mn(II) coordination polymers, [Mn3(IDPA)3(DMA)(H2O)2]n·n[(H2O)(DMA)] (1), [Mn(IDPA)(2,2′-bpy)(H2O)]n·2n(H2O) (2), [Mn(IDPA)(phen)(H2O)]n (3), [Mn(IDPA)(bpa)1/2(H2O)2]n·n(H2O) (4), and [Mn(IDPA)(4,4′-bpy)1/2]n (5) [H2IDPA = 5-(1-oxoisoindolin-2-yl) isophthalic acid, bpy = bipyridine, bpa = 1,2-bis(4-pyridyl)ethane, phen = 1,10-phenanthroline, DMA = N,N-dimethylacetamide], have been synthesized with different N-donor ligands under solvothermal conditions and structurally characterized. The crystal structures of 1–5 illustrate that hydrogen bonds and π–π interactions play critical roles in the construction of the extended supramolecular architectures. Compound 1 possesses a two-dimensional (2D) layer structure with a uninodal 4-connected sql tetragonal plane net. Compounds 2–4 feature one-dimensional chain (1D) structures, which further extend to 2D supramolecular networks via intermolecular π–π interactions and hydrogen bonds. Compound 5 exhibits a most remarkable and unique three-dimensional (3D) framework with a binodal (4,5)-connected new topology with the Schläfli symbol of {42·52·62}{42·53·64·7}. Interestingly, the carboxylic groups of H2IDPA display six different types of coordination modes in 1–5 and the steric bulk of H2IDPA plays an important role in influencing the structures of its compounds. Compound 1 containing triangular trinuclear (Mn1⋯Mn2⋯Mn3) units displays weak antiferromagnetic interactions in the system, whereas compounds 2–5 show that the overall magnetic interactions among the Mn(II) ions are weakly ferromagnetic. Besides, the thermal stabilities and luminescence properties of 1–5 have also been investigated and discussed in detail.
Co-reporter:Zhiqiao Wang;Zhongning Xu;Siyan Peng;Zhangfeng Zhou;Pengbin Pan;Lin Lin;Yeyan Qin;Guocong Guo;Yuangen Yao
Chinese Journal of Chemistry 2017 Volume 35(Issue 6) pp:759-768
Publication Date(Web):2017/06/01
DOI:10.1002/cjoc.201600746
Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences has achieved the industrialization of the first generation catalysts for coal to ethylene glycol for the first time in 2009. However, there are still lots of aspects to be improved, such as high noble metal loading and toxic Cr in catalyst of ester hydrogenation. To improve the catalysts, we have done systematic deep research about the nanostructures of catalysts, and revealed facet effect, size effect, synergistic effect, support effect, and so on. A series of catalysts preparation technologies have been developed to achieve the efficient utilization of noble metals. The Pd loadings of dehydrogenation catalyst and CO oxidative coupling catalyst have been dropped from 2.5% to 0.9% and 2.0% to 0.13%, respectively, while the catalytic performances are enhanced greatly. The toxic Cu-Cr in ester hydrogenation catalyst has been upgraded to green Cu-Si. The new catalysts for coal to ethylene glycol with advancement have been successfully developed with independent intellectual property rights.
Co-reporter:Run-Ping Ye, Ling Lin, Jin-Xia Yang, Ming-Ling Sun, Fei Li, Bin Li, Yuan-Gen Yao
Journal of Catalysis 2017 Volume 350(Volume 350) pp:
Publication Date(Web):1 June 2017
DOI:10.1016/j.jcat.2017.02.018
•Dextrin is applied for the first time in Cu–SiO2 catalysts.•The EG yield of 0.05D-Cu–SiO2 is four times higher than that of Cu–SiO2 at 463 K.•The EG selectivity of 0.05D-Cu–SiO2 could stay above 95% after 200 h.•More CuO and Cu–O–Si units were present, while copper phyllosilicate decreased in catalysts.The influence of low-cost dextrin coating on the performance of Cu–SiO2 catalysts for the vapor-phase hydrogenation of dimethyl oxalate (DMO) to ethylene glycol (EG) was systematically investigated. On the 0.05D-Cu–SiO2 catalyst, 99.8% DMO conversion and 92.3% EG selectivity could be obtained at 463 K under 2.0 g g-catal−1 h−1 weight liquid hourly space velocity, which is almost four times higher than that of the catalyst without coating with dextrin. Characterization methods including N2 physisorption, XRD, TEM, H2 TPR, and XPS were carried out to elucidate the structure–performance relationship. Experimental results indicated that copper phyllosilicate contents decreased while well-dispersed CuO and Cu–O–Si units increased. The improved morphology with more compact nanosized crystalline copper structure resulted in more Cu+ species, which lead to better DMO conversion and EG selectivity in a long-term stability test.Download high-res image (119KB)Download full-size image
Co-reporter:Run-Ping Ye, Xin Zhang, Lei Zhang, Jian Zhang, and Yuan-Gen Yao
Crystal Growth & Design 2016 Volume 16(Issue 7) pp:4012-4020
Publication Date(Web):June 14, 2016
DOI:10.1021/acs.cgd.6b00548
Three Cd(II) supramolecular isomers, namely, [Cd(IDPA)(H2O)]n·2n(H2O) (1), [Cd2(IDPA)2(H2O)3]n·n(DMF)·4n(H2O) (2), [Cd3(IDPA)3(DMA)(H2O)2n]·n(DMA)·n(H2O) (3), and two Cu(II) isomorphic complexes including [Cu(IDPA) (DMF)]n (4) and [Cu(IDPA)(H2O)]n (5) (DMF = N,N-dimethylformamide; DMA = N,N-dimethylacetamide; H2IDPA = 5-(1-oxoisoindolin-2-yl) isophthalic acid), have been synthesized under similar solvothermal conditions with different solvent systems and pH values. However, complexes 1 and 3 share an unanticipated 2D layered structure while complex 2 presents an unprecedent topological network with a new point symbol of {4·62}{4·67·82}. Complexes 4 and 5 have been generated from [Cu2(COO)4] paddlewheels as the 4-connected node with the point symbol of {64·82}. The diverse structures of 1–5 can be much related with hydrogen bonds and π–π interactions. Furthermore, the luminescent properties of complexes 1–3 have been investigated before-and-after desolvation by heating at 220 °C for 2 h. Interestingly, the quantum yield of complex 2 is changed from 37.20% to 10.73% after desolvation. These results indicate that solvent molecules actually enhance the photoluminescence instead of quenching it. The construction of these complexes shows that the solvent and pH value can regulate the crystal structure and luminescent properties.
Co-reporter:Jin-Xia Yang, Ji-Quan Zhai, Xin Zhang, Ye-Yan Qin and Yuan-Gen Yao
Dalton Transactions 2016 vol. 45(Issue 2) pp:711-723
Publication Date(Web):04 Nov 2015
DOI:10.1039/C5DT03731J
Taking advantage of the conformational flexibility of the bpp ligand and aliphatic dicarboxylic acids, six interesting entangled coordination polymers, {[Cd(fum)(bpp)(H2O)]·(H2O)}n (1), {[Cd(fum)(bpp)2]·(H2O)5}n (2), {[Cd2(suc)1.5(bpp)2(NO3)(H2O)2]·6H2O}n (3), {[Cd(suc)(bpp)2]·(H2O)1.5}n (4), {[Cd2(glu)2(bpp)3]·10H2O}n (5), and {Cd(adp)(bpp)(H2O)}n (6) have been prepared and structurally characterized (bpp = 1,3-bi(4-pyridyl)propane, fum = fumaric, suc = succinate, glu = glutaric, adp = adipic). Compounds 1 and 2 are comprised of undulated 2D 44-sql networks. In the structure of compound 1, two identical undulated layers are parallelly interpenetrated with each other to give a 2D → 2D interpenetrating framework. For 2, the dangling arms projected from 2D layers are intercalated into the neighboring sheets, producing a 2D → 3D polythreading framework. Compound 3 shows a rare example of a 2D self-penetrating framework with a (3,4)-connected (42·63·8)(42·6) topology. Compound 4 presents an unusual 2D self-threading network with a novel 4-connected {42·63·8} topology. Compound 5 displays a 3D self-penetrating system based on a 2D → 3D parallel polycatenation array. Compound 6 exhibits an unprecedented 3D self-penetrating structure having both 1D + 1D → 1D polycatenation and 3D + 3D → 3D interpenetration characteristics. A comparison of these six compounds demonstrates that both the different spacer lengths of the aliphatic dicarboxylates and reactant ratios appear to play a significant role in the assembly of entangled frameworks. In addition, thermal stabilities and photoluminescence properties of 1–6 have been examined in the solid state at room temperature.
Co-reporter:Run-Ping Ye, Ling Lin, Yuan-Gen Yao
Inorganica Chimica Acta 2016 Volume 453() pp:8-15
Publication Date(Web):1 November 2016
DOI:10.1016/j.ica.2016.07.045
•Four novel CPs based on a new semi-rigid multicarboxylate ligand with the help of three auxiliary ligands.•Compounds 1 and 2 display weak antiferromagnetic interactions in the system.•Compound 3 is a 2D layer structure and its QY is largely increased to 22.52% compared to free ligand (QY = 4.41%).•Compound 4 shows a white light emission.Four interesting coordination polymers, namely [Co(IDPA)(phen)(H2O)]n (1), [Co(IDPA)(bpp)(H2O)]n·2n(H2O) (2), [Zn(IDPA)(py)]n (3), and [Pb(IDPA)(H2O)]n (4) (H2IDPA = 5-(1-oxoisoindolin-2-yl)isophthalic acid, phen = 1,10-phenanthroline, bpp = 1,3-bis(4-pyridyl)propane, py = pyridine), have been successfully synthesized under solvothermal conditions and structurally characterized. Single-crystal X-ray diffraction analyses indicate that compound 1 shows a zigzag chain, while compounds 2–4 exhibit two-dimensional wavelike or flat layer structures with the same uninodal 4-connected sql topology. These results reveal that different metal centers with the presence of auxiliary ligands maybe play a significant role in the construction process of coordination polymer. Furthermore, compounds 1 and 2 display weak antiferromagnetic interactions in the system. Interestingly, because H2IDPA is a coplanar ligand with large rigid π-conjugated system, it exhibits a strong blue emission with the quantum yield (QY) up to 4.41%. Furthermore, compound 3 is a 2D layer structure and its QY is largely increased to 22.52%. Besides, compound 4 shows a multiple emissions from blue to yellow and falls within the white region of the 1931 CIE chromaticity diagram. Therefore, it is suggested to turn on the fluorescence by building the fluorophore within metal-organic frameworks.Four interesting MOFs were obtained via the assembly of a novel H2IDPA ligand with different metal ions, in which the resultant products have excellent magnetic properties and strong luminescence with a high quantum yield of 22.52%.
Co-reporter:Run-Ping Ye, Jin-Xia Yang, Xin Zhang, Lei Zhang, Yuan-Gen Yao
Journal of Molecular Structure 2016 Volume 1106() pp:192-199
Publication Date(Web):15 February 2016
DOI:10.1016/j.molstruc.2015.10.086
•Four compounds based on a new semirigid tricarboxylate ligand, which has been rarely reported before.•These compounds display four different structures varying from OD to 2D.•Compounds 1–4 exhibit strong blue luminescence at room temperature.By reacting an asymmetry semi-rigid V-shaped linker H3L (H3L = 3-(3-carboxyphenoxy) phthalic acid) and Zn(NO3)2·6H2O under different N-donor ligands in different solvents, four new Zn-based coordination polymers, [Zn(HL)(2,2′-bpy)(H2O)]n(1), [Zn(HL)(4,4′-bpy)]n·n(DMA) (2), [Zn3(L)2(phen)3(H2O)]n·n(H2O) (3) and [Zn(HL)(phen)(H2O)]2(4) (2,2′-bpy = 2,2′-bipyridine; 4,4′-bpy = 4,4′-bipyridine; phen = 1,10-phenanthroline; DMA = N,N-dimethylacetamide) have been obtained. All of these compounds have been clearly identified by single crystal X-ray diffraction analysis. Compound 1 exhibits one-dimensional (1D) chain structure constructed from uninuclear Zn(II) motif, which further extends into 2D supramolecular architecture via intermolecular π–π interactions and hydrogen bonds. Structural analysis reveals that the structure of 2 and 3 can be described as a 2D hcb topology network with the point symbol of {63}. Compound 4 shows a 0D binuclear motif while its 3D packing network has a large potential solvent voids. The results of this research demonstrate that the solvent and the secondary ligands could co-regulate different structural coordination polymers with interesting properties. In addition, the thermal stabilities and solid-state luminescence properties of compounds 1–4 have also been investigated.Presented here are four MOFs based on a new semirigid tricarboxylate ligand. Of particular interest is that the four compounds are co-regulated by different auxiliary N-donor ligands and solvents.
Co-reporter:Dr. Luyang Qiao;Dr. Qiaohong Li;Dr. Zhangfeng Zhou; Rui Si; Yuangen Yao
ChemCatChem 2016 Volume 8( Issue 11) pp:1909-1914
Publication Date(Web):
DOI:10.1002/cctc.201600301
Abstract
Preferential oxidation of the H2 impurity in CO streams is crucial for the catalytic conversion of CO into ethylene glycol. It is uncertain as to whether H2 can overthrow the dominance of CO and finally lead the reaction. Not only is this a typical research issue, but it is also extremely critical for practical applications. So far, no catalyst has shown selectivity higher than 50 % owing to competitive adsorption of CO. In this work, we report a PdClx-based catalyst that can readily overcome the challenge mentioned above. Over this catalyst, the selectivity of H2 oxidation is promoted by more than 40 % relative to that over the conventional Pd/Al2O3 catalyst and reaches a value of 87 %. The turnover frequency of undesired CO oxidation is inhibited by at least one order of magnitude. We found that the reconstructed palladium chloride was highly selective to this reaction by facile inhibition of the adsorption and oxidation of CO.
Co-reporter:Run-Ping Ye, Xin Zhang, Ji-Quan Zhai, Ye-Yan Qin, Lei Zhang, Yuan-Gen Yao and Jian Zhang
CrystEngComm 2015 vol. 17(Issue 47) pp:9155-9166
Publication Date(Web):23 Oct 2015
DOI:10.1039/C5CE01884F
A series of Zn/Cd(II) coordination polymers, namely, [Zn(IDPA)(H2O)]n·n(H2O) (1), [Cd(IDPA)(bpp)]n·n(H2O) (2), [Cd(IDPA)(4,4′-bpy)1/2]n (3), [Zn(IDPA)(4,4′-bpy)1/2]n (4), [Zn4(IDPA)4(phen)2·(H2O)2]n·2n(H2O) (5), [Zn(IDPA)(phen)·(H2O)]n·n(H2O) (6) and [Zn(IDPA)(2,2′-bpy)·(H2O)]n·n(H2O) (7), have been prepared on the basis of a bulky 1,3-benzenedicarboxylate derivative ligand, 5-(1-oxoisoindolin-2-yl)isophthalic acid (H2IDPA), with the help of 1,3-bis(4-pyridyl)propane (bpp), 4,4′-bipyridine (4,4′-bpy), 1,10-phenanthroline (phen) or 2,2′-bipyridine (2,2′-bpy) as a secondary ligand. H2IDPA is a luminous ligand with a large rigid π-conjugated system, and the solid-state luminescence properties of compounds 1–7 have been comparatively investigated. The results indicate that their luminescence properties have been enhanced compared to those of the free ligand, especially for compounds 2–7 which have been further regulated by N-donor ligands with a π-conjugated system. Compound 2 is a 2D layer structure, and its quantum yield (QY) is 39.80%, which is much higher than those of the H2IDPA ligand (QY = 4.41%) and compound 1 (QY = 6.32%). From the viewpoint of crystal structure diversity and comparison, our results further demonstrate that ligands with a large π-conjugated system have a promotional effect on luminescence properties of coordination polymers.
Co-reporter:Jin-Xia Yang, Ye-Yan Qin, Jian-Kai Cheng, Xin Zhang, and Yuan-Gen Yao
Crystal Growth & Design 2015 Volume 15(Issue 5) pp:2223-2234
Publication Date(Web):March 26, 2015
DOI:10.1021/cg501879w
By employing a variety of different aliphatic dicarboxylic acids as the secondary auxiliary ligands, six novel zinc compounds, namely, {[Zn2(mal)2(bix)1.5]·3H2O}n (1), {[Zn2(male)2(bix)2]·3H2O}n (2), {[ Zn3(suc)2(bix)4]·2NO3·7H2O}n (3), {Zn(glu)(bix)]·2H2O}n (4), {Zn(fim)(bix)]·2H2O}n (5), and {Zn(sub)(bix)]·3H2O}n (6) (mal = malonic, male = maleate, suc = succinate, glu = glutaric, fim = pimelic, sub = suberate, bix = 1,4-bis(imidazol-1-ylmethyl)-benzene) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction analyses, and further characterized by infrared spectra, elemental analyses, powder X-ray diffraction, and thermogravimetric analyses. Compound 1 exhibits an extremely rare example of 1D rotaxane-like chain. Compound 2 features a novel 4-connected {65·8} topology. Compound 3 shows an unprecedented two-level hierarchical self-penetrating system based on unusual 2D + 2D → 2D and 1D + 2D → 3D polyrotaxane array. Both compounds 4 and 5 are comprised of undulated 2D 44-sql networks. In 4, the adjacent undulated layers are parallel interpenetrated to each other to give a 2D → 3D polycatenation framework, which further constructs a 3-fold interpenetrating pcu network through extensive hydrogen bonding. In compound 5, there are only two identical undulated layers which are interpenetrated to each other to give a 2D → 2D parallel interlocked structure. Compound 6 displays a 4-connected non-interpenetrating cds network. Structural diversity of these six complexes indicates that the conformation of bix ligand and the spacer length of aliphatic dicarboxylic anions play an important role in the assembly of different frameworks. Furthermore, the solid-state luminescent properties of compounds 1–6 have also been investigated at room temperature.
Co-reporter:Qiaohong Li, Zhangfeng Zhou, Ruiping Chen, Baozhen Sun, Luyang Qiao, Yuangen Yao and Kechen Wu
Physical Chemistry Chemical Physics 2015 vol. 17(Issue 14) pp:9126-9134
Publication Date(Web):23 Feb 2015
DOI:10.1039/C4CP05738D
Oxidative coupling of toxic pollutant CO to form the platform raw chemical material dimethyl oxalate (DMO) has been industrialized however the catalytic mechanism has been unknown so far. The reaction mechanism of CO oxidative coupling to form DMO on a Pd(111) surface has been investigated using density functional theory (DFT) and in situ diffuse reflectance infrared (DRIR) spectroscopy. DFT calculations and in situ DRIRS measurements indicate that two co-adsorbed intermediates COOMe and OCCO, initiate the reaction. C–C coupling occurs earlier due to a low coupling barrier and small steric hindrance. The results also suggest that Pd(111) is selective towards DMO over DMC, and that CO pre-adsorption and CO in excess effectively enhance the yield of DMO. The microscopic elucidation of this important reaction suggests improvements in coal-to-EG (CTEG) production which can be applied in practice to effectively enhance the yield and reduce the cost. The results may help with further fine-tuning and designing of high-efficient noble metal catalysts.
Co-reporter:De-Liang Yang, Xin Zhang, Yuan-Gen Yao and Jian Zhang
CrystEngComm 2014 vol. 16(Issue 34) pp:8047-8057
Publication Date(Web):08 Jul 2014
DOI:10.1039/C4CE01032A
Five new coordination polymers, namely [Cd3(dcppa)(Hdcppa)(H2O)]·(Me2NH2)·(DMA)2 (1), [CdCa(dcppa)(DMA)2] (2), [CdCa(dcppa)(H2O)2(DMA)] (3), [Ba2(H2dcppa)2(μ2-H2O)(H2O)(DMA)]·(H2O) (4), and [Ba2(H2dcppa)2(μ2-H2O)(H2O)(DMF)]·(H2O) (5) (Me2NH2+ = dimethylammonium cation; DMA = N,N-dimethylacetamide; DMF = N,N-dimethylformamide; H4dcppa = 3-(3′,5′-dicarboxylphenoxy) phthalic acid), were synthesized under solvothermal conditions and structurally characterized. Compound 1 presents a unique binodal (3,6)-connected {43}2{47·88} topology structure, which is a 2D layer anionic network with Me2NH2+ cations occupying the voids, built upon a trinuclear Cd3 unit. Compounds 2 and 3 are all bimetallic Cd–Ca compounds consisting of tetranuclear Cd2Ca2 units extending to a 3D (3,6)-connected rtl topology structure and a 2D (3,6)-connected kgd topology structure, respectively. Compounds 4 and 5 are isostructural and exhibit an unprecedented 3D (4,10)-connected topology structure in which a 1D infinite barium chain is observed. From the viewpoint of crystal structure diversity and comparison, our results further demonstrate that the coordination modes of metal ions and ligands are the vital elements in forming the final crystal structure. In addition, the thermal stabilities and solid-state luminescence properties of compounds 1–5 are also discussed.
Co-reporter:Jin-Xia Yang, Ye-Yan Qin, Jian-Kai Cheng, and Yuan-Gen Yao
Crystal Growth & Design 2014 Volume 14(Issue 3) pp:1047-1056
Publication Date(Web):January 17, 2014
DOI:10.1021/cg401519w
Via hydrothermal synthesis, the self-assembly of Zn(II) ions and H2fum with four flexible N-donor ligands, bpp, bib, bix, and bmix, generated five interesting entanglement systems (H2fum = fumaric acid, bpp = 1,3-bi(4-pyridyl)propane, bib = 1,4-bis(N-imidazolyl)butane, bix = 1,4-bis(imidazol-1-ylmethyl)-benzene, bmix = 1,4-bis(2-methylimidazol-1-ylmethyl)-benzene): {[Zn(fum)(bpp)]·H2O}n (1), {[Zn(fum)0.5(bib)1.5(H2O)]·NO3·3H2O}n (2), {Zn(fum)(bib)}n (3), {[Zn2(fum)2(bix)2]·3H2O}n (4), and {[Zn(fum)(bmix)0.5]·0.5H2O}n (5). Their structures have been determined by single-crystal X-ray diffraction analyses, elemental analyses, IR spectra, X-ray powder diffraction (XRPD), and thermogravimetric (TG) analyses. Compound 1 exhibits a rare 3D self-penetrating network with an unprecedented (85·10) topology. Compound 2 features a normal mode of 4-fold diamondoid interpenetrating net. However, in compound 3, five diamond networks interweave to form an interpenetrated diamond framework in an “abnormal” [3 + 2] mode. Compound 4 crystallizes in the orthorhombic crystal system and chiral space group P212121, which can be defined as an unusual 4-fold [2 + 2] interpenetrated unc-c net. Compound 5 displays a 2-fold interpenetrated 3D network with the classical pcu topology. A comparison of all compounds demonstrates that the structural characteristics of flexible N-donor ligands play a great role in the assembly of such different frameworks. Moreover, the luminescent properties of compounds 1–5 in the solid state have also been investigated.
Co-reporter:Ming-Ling Sun, Xin Zhang, Yuan-Yuan Huang, Qi-Pu Lin, Ye-Yan Qin and Yuan-Gen Yao
New Journal of Chemistry 2014 vol. 38(Issue 1) pp:55-58
Publication Date(Web):03 Oct 2013
DOI:10.1039/C3NJ00981E
Three isomorphous homochiral 3D lanthanide coordination polymers ([Ln(HCOO)(D-cam)]n, where Ln = Dy (1), Ho (2), Er (3)), featuring sra topology have been constructed from triple-strand helical {Ln–O}n rod SBUs and chiral D-cam spacers. Thermogravimetric analyses show the remarkable thermal stabilities of all three rigid lanthanide camphorate frameworks up to 450 °C.
Co-reporter:De-Liang Yang, Xin Zhang, Jin-Xia Yang, Yuan-Gen Yao, Jian Zhang
Inorganica Chimica Acta 2014 Volume 423(Part A) pp:62-71
Publication Date(Web):1 November 2014
DOI:10.1016/j.ica.2014.07.054
•Five novel coordination polymers based on a new semirigid multicarboxylate ligand.•These compounds display five different heterometallic tetranuclear Zn2M2 units.•It exhibits strong yellow luminescence at room temperature.Five novel three-dimensional (3D) heterometallic coordination polymers, [ZnCa(dcppa)(DMF)2]n (1), [ZnCa(dcppa)(DMA)2]n (2), [ZnBa(dcppa)(DMF)2]n (3), [ZnBa(dcppa)(DMA)2]n (4), and [ZnNa(dcppa)(DMF)]n·n(Me2NH2)·n(H2O)2 (5) (Me2NH2+ = dimethylammonium cation; DMA = N,N-dimethylacetamide; DMF = N,N-dimethylformamide; H4dcppa = 3-(3′,5′-dicarboxylphenoxy) phthalic acid), have been hydrothermally synthesized and structurally characterized with the aid of single-crystal X-ray diffraction. Complexes 1–5 are heterometallic Zn/M (M = Ca, Ba, Na) coordination polymers constructed from a semirigid H4dcppa ligand and tetranuclear metal clusters. Topological analyses show that 1/3/4 and 2/5 exhibit complicated 3D framework that could be simplified into binodal (3,6)-connected rtl nets and binodal (3,6)-connected flu nets, respectively. Unlike 1–4, 5 features a unique 3D anionic framework with Me2NH2+ cations occupying the voids. From the viewpoint of crystal structure diversity and comparison, our results further prove that the coordination modes of metal ions and ligands play indispensable roles in the construction of the final crystal structure. Moreover, the thermal stability and solid-state luminescence properties of 1–5 have also been investigated at room temperature.Presented here are a series of bimetallic Zn/M (Ca, Ba, Na) MOFs based on a semirigid multicarboxylate ligand and tetranuclear metal clusters. Of particular interest is that the five compounds are 3D frameworks with (3,6)-connected rtl/flu topologies.
Co-reporter:Xin Zhang, Yuan-Yuan Huang, Qi-Pu Lin, Jian Zhang and Yuan-Gen Yao
Dalton Transactions 2013 vol. 42(Issue 6) pp:2294-2301
Publication Date(Web):12 Oct 2012
DOI:10.1039/C2DT31536J
Alkaline-earth metal ions were used to tune four new heterometallic frameworks, {[Cd2.07Mg0.93(BTC)2(H2O)4]·2H2O}n (1), {[Cd2Ca(BTC)2(H2O)4]·2H2O}n (2), {[Cd2Sr(BTC)2(H2O)5]·H2O}n (3) and [Cd6Ba3(BTC)3(H2O)10]n (4) (H3BTC = 1,3,5-benzenetricarboxylic acid), synthesized from H3BTC and the corresponding metal salts. Single-crystal X-ray analysis shows that compound 1 is a three-dimensional (3D) framework based on heterometallic Cd–O–Cd–O–Mg inorganic chain subunits, compounds 2 and 3 are basically isostructural and feature a 3D framework based on Ca(II) or Sr(II) polyhedrons decorated with Cd–O–Cd inorganic chains. Compound 4 is a 3D framework templated by disordered inorganic hydrate Ba(II) ions, and also features inorganic Cd–O–Cd chains, which are connected together through corner sharing with the {Cd1O6} polyhedrons by {Ba1O6} polyhedrons, giving rise to a rare heterometallic 3D inorganic skeleton. Moreover, the solid-state fluorescence of compounds 1–4 and NLO properties of compounds 2–4 have also been investigated at room temperature.
Co-reporter:Yuan-Yuan Huang, Xin Zhang, Yuan-Gen Yao
Inorganica Chimica Acta 2013 Volume 397() pp:38-41
Publication Date(Web):1 March 2013
DOI:10.1016/j.ica.2012.11.015
A new heterometallic compound, namely [CdBa2(m-BDC)2(DMF)4(NO3)2]n (1 m-H2BDC = isophthalic acid), has been successfully synthesized from m-BDC ligand and corresponding metal salts. Single-crystal X-ray diffraction analysis revealed that 1 is a three-dimensional (3D) framework containing heterometallic trinuclear [CdBa2(COO)4] clusters as building subunits and can be simplified into a 4-connected dia net with the schäfli symbol of 66. Of particular interest is that it also features a rare 3D inorganic connectivity. Moreover, this compound exhibits strong yellow luminescence in the solid state at room temperature.Graphical abstractPresented here is a new heterometallic coordination polymer, [CdBa2(m-BDC)2(DMF)4]n (1 m-H2BDC = isophthalic acid), consists of heterometallic trinuclear [CdBa2(COO)4] clusters as SBUs, which features a rare 3D inorganic connectivity.Highlights► New heterometallic coordination polymer containing heterometallic [CdBa2(COO)4] clusters as SBUs. ► It features a rare 3D inorganic connectivity. ► It exhibits strong yellow luminescence at room temperature.
Co-reporter:Xin Zhang, Yuan-Yuan Huang, Yuan-Gen Yao
Inorganic Chemistry Communications 2013 Volume 28() pp:49-51
Publication Date(Web):February 2013
DOI:10.1016/j.inoche.2012.10.041
The self-assembly of pyridinecarboxylate ligand (H2L) with mixed metal ions under hydrothermal conditions afforded a new heterometallic coordination polymer, [DyAg(L)2(H2O)]n·2n(H2O) (1 H2L = 5-(pyridine-4-ylmethoxy)-isophthalic acid). Single-crystal X-ray diffraction analysis reveals that 1 features an unusual three-dimensional (3D) pillar-layer framework with an unprecedented (3,4,5)-connected topology. Interestingly, each individual structure is interpenetrated by another identical one.Presented here is a new heterometallic coordination polymer, [DyAg(L)2(H2O)]n·2n(H2O) (1 H2L = 5-(pyridine-4-ylmethoxy)-isophthalic acid), which features an unusual 3D pillar-layer framework with an unprecedented (3,4,5)-connected topology.Highlights► New heterometallic coordination polymer based on T-shaped pyridinecarboxylate ligand. ► It features an unusual 3D pillar-layer framework. ► It presents an unprecedented (3,4,5)-connected topology.
Co-reporter:Xin Zhang, Ming-Ling Sun, Yuan-Yuan Huang, Yuan-Gen Yao
Inorganic Chemistry Communications 2013 Volume 37() pp:155-157
Publication Date(Web):November 2013
DOI:10.1016/j.inoche.2013.09.058
•New Zn(II) coordination polymer based on pbdc and TAZ.•New (4,8)-connected topology.•It emits intense luminescence at room temperature.A new compound, namely [Zn2(pbdc)1.5(TAZ)]n 2nH2O (1 H2pbdc = terephthalic acid, HTAZ = 1H-1,2,4-triazole), has been hydrothermally synthesized from H2pbdc, HTAZ and Cd(II) salts. Single crystal X-ray diffraction analysis reveals that compound 1 represents an unprecedented (4,8)-connected 3D topological network. Notably, two TAZ ligands in uniform μ3-1,2,4 bridging mode connect four Zn(II) ions together, giving rise to a [Zn4(TAZ)2] metallo-ligand subunit, which are further bridged via pbdc ligands in two kinds of coordination modes, resulting in the final 3D complicated framework. The relevant density of states (DOS) calculation result showed that the luminescence of 1 mainly originates from HTAZ intraligand charge transition.Presented here is a new luminescent Zn(II) coordination polymer, namely [Zn2(pbdc)1.5(TAZ)]n (1 H2pbdc = terephthalic acid, HTAZ = 1H-1,2,4-triazole), which represents an unprecedented (4,8)-connected topological network.
Co-reporter:Xin Zhang, Yuan-Yuan Huang, Jian-Kai Cheng, Yuan-Gen Yao, Jian Zhang and Fei Wang
CrystEngComm 2012 vol. 14(Issue 14) pp:4843-4849
Publication Date(Web):01 May 2012
DOI:10.1039/C2CE25440A
Alkaline earth metal ion doped Zn(II)-terephthalates, [Zn2Mg(PBDC)3(DMA)2]n (1), [ZnCa(PBDC)2(DMA)2]n (2), [ZnSr(PBDC)2(DMA)2]n (3) and [Zn2Ba(PBDC)3(μ2-O1w)2(DMF)]n·n(DMF) (4) (H2PBDC = terephthalic acid, DMA = N,N′-dimethylacetamide, DMF = N,N′-dimethylformamide), have been solvothermally synthesized and characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, IR spectra, and thermal analyses. Different secondary building subunits, [Zn2Mg(μ2-COO)3] for 1, [ZnCa(μ2-COO)3] for 2, [ZnSr(μ2-COO)3] for 3, and [Zn2Ba(μ2-COO)4(μ2-O1w)2] for 4, are realized by the introduction of different alkaline earth ions. Compound 1 is a two-dimensional (2D) layer structure with 6-connected hxl topology. Compounds 2 and 3 are isostructural and exhibit a three-dimensional (3D) framework with (3,5)-connected {4.62}{4.66.83} topology owing to their similar secondary building subunits. Compound 4 is a three-dimensional (3D) opened framework with the channels occupied by the disordered lattice DMF molecules and can be simplified into a (3,8)-connected {42.6}2{44.614.78.82} topology. Moreover, the solid-state fluorescence of compounds 1–4 have also been investigated at room temperature.
Co-reporter:Jin-Xia Yang, Xin Zhang, Jian-Kai Cheng, Jian Zhang, and Yuan-Gen Yao
Crystal Growth & Design 2012 Volume 12(Issue 1) pp:333-345
Publication Date(Web):November 14, 2011
DOI:10.1021/cg201143f
Five new Zn(II)/ODPT/bpe compounds, namely, {[Zn(bpe)(H2O)2](H2ODPT)·3H2O}n (1), {[Zn4(ODPT)2(bpe)3(H2O)2]2(bpe)·7H2O}n (2), {[Zn2(ODPT)(bpe)2]2·7H2O}n (3), {Zn4(ODPT)2(bpe)}n (4), and {Zn2(ODPT)(bpe)(H2O)2}n (5) (ODPT = 4,4′-oxidiphthalate, bpe =1,2-bis(4-pyridyl)ethane), have been synthesized through a hydrothermal method under different pH conditions, and characterized by single-crystal X-ray diffraction, element analysis, infrared spectra (IR), and thermogravimetric (TG) analyses. Compound 1 shows a 3D network framework constructed by the 1D linear [Zn(bpe)(H2O)4]n2+ cationic chains through extensive hydrogen-bonding. Compound 2 displays an unusual three-dimensional (3D) meso-racemic self-penetrating coordination network with distinct chiral information in the interpenetrating networks. Compound 3 features a novel 4-connected (4·62·83)(42·62·82) topology, also exhibiting an intriguing 3D self-penetrating structure formed by triple- and double-stranded helical chain motifs. Compounds 4 and 5 are based upon 3D pillared-layer frameworks constructed from Zn2+ and ODPT4-, and further consolidated by the bpe ligands as molecular pillars. The most striking feature of 5 is that achiral ODPT4– ligands link the Zn cations into right-handed 21 helical chains, and the chiral information is transferred to the 3D framework with a chiral space group C2221. The diversity of the product structures illustrates the marked sensitivity of the coordination chemistry of the V-shaped multicarboxylate ligand (H4ODPT) to the pH value of the solution. Moreover, the thermal dynamic properties and fluorescent properties of all compounds are also investigated.
Co-reporter:Xin Zhang, Yuan-Yuan Huang, Ming-Jian Zhang, Jian Zhang, and Yuan-Gen Yao
Crystal Growth & Design 2012 Volume 12(Issue 6) pp:3231-3238
Publication Date(Web):May 8, 2012
DOI:10.1021/cg3003756
Solvothermal reactions of Ca(NO3)2 or Ba(NO3)2 with aromatic carboxylate ligands afforded four new inorganic–organic hybrid frameworks, [Ca(PBDC)(H2O)3]n (1), [Ca(OBDC)(H2O)]n (2), [Ba5(OBDC)4(H2O)2(NO3)2]n (3), and [Ba3(BTC)2(H2O)4]n (4) (H2PBDC = terephthalic acid, H2OBDC = phthalic acid, H3BTC = 1,3,5-benzenetricarboxylic acid). These compounds have been fully characterized by single crystal X-ray diffraction, powder X-ray diffraction, satisfactory elemental analysis, IR spectra, and TG analysis. X-ray analysis shows that compound 1 features a one-dimensional chain (1D) structure with the I1O0 connectivity, both compound 2 and compound 3 feature a two-dimensional (2D) layer structure with the I1O1 connectivity, I2O0 connectivity, respectively, compound 4 features a three-dimensional (3D) framework with a rare I3O0 connectivity. Thermal stabilities and luminescent properties of compounds 1–4 and NLO property of compound 4 have also been investigated.
Co-reporter:Jian-Kai Cheng, Xin Zhang, Ming-Jian Zhang, Yuan-Gen Yao
Inorganic Chemistry Communications 2012 Volume 17() pp:88-90
Publication Date(Web):March 2012
DOI:10.1016/j.inoche.2011.12.021
A rare Pb(II) arene coordination polymer,[Pb(bimS)] (1; HbimSH = 2-mercaptobenzimidazole), has been solvothermally synthesized and characterized by single crystal X-ray diffraction, XRD, TGA, PL(photoluminescene), and UV–vis diffuse reflective spectra. The band structure and the densities of states of the title compound have been calculated to further understand the relation between the structure and optical property.An Exceptionally Stable Pb(II) Arene coordination polymer has been solvothermally synthesized and characterized by X-ray diffraction, XRD, TGA, PL(photoluminescene), and UV–vis diffuse reflective spectra. The band structure and the densities of states of the title compound have been calculated to further understand the relation between the structure and the optical property.Highlights► An exceptionally stable Pb(II) arene coordination polymer has been synthesized. Photoluminescence and UV-vis diffuse reflective spectra have been performed. ► The band structure and the densities of states have been calculated.
Co-reporter:Xin Zhang, Zhao-Ji Li, Ye-Yan Qin, Yuan-Gen Yao
Inorganic Chemistry Communications 2012 Volume 15() pp:1-4
Publication Date(Web):January 2012
DOI:10.1016/j.inoche.2011.08.023
A luminescent compound, [Cd (HO-BDC) (bpe)1.5]n (1 HO-H2BDC= 5-hydroxyisophthalic acid, bpe=1,2-bis (4-pyridyl) ethane), was hydrothermally synthesized. It features a 5-connected two-dimensional (2D) double layer motif. Interestingly, this 2D double layer motif is further interlocked with the neighboring ones in the parallel fashion, giving rise to the final three-dimensional (3D) polycatenated network. Moreover, the title compound exhibits intense yellow photoluminescence at room temperature.Presented here is a novel photoluminescent Cd(II) coordination polymer, [Cd (HO-BDC) (bpe)1.5]n (1 HO-H2BDC= 5-hydroxyisophthalic acid, bpe=1,2-bis (4-pyridyl) ethane), which features a 5-connected two-dimensional (2D) bilayer motif. Interestingly, this 2D bilayer is further interlocked with the adjacent ones, giving rise to a three-dimensional (3D) polycatenated network.Highlights► New Cd(II) compound with 5-connected two-dimensional double layer ► New Cd(II) compound features 2D → 3D polycatenated structure ► This compound exhibits intense yellow photoluminescence at room temperature.
Co-reporter:Yuan-Yuan Huang, Xin Zhang, Jian-Kai Cheng, Yuan-Gen Yao
Inorganic Chemistry Communications 2012 Volume 23() pp:6-8
Publication Date(Web):September 2012
DOI:10.1016/j.inoche.2012.05.016
A new Sr(II) doped Cd(II)-tartrate, namely [Cd3Sr(L-tart)4]n (1 L-tart = L-tartrate acid), interestingly, featuring two different layers, was hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Compound 1 is the first heterometallic coordination polymer based on L-tart and exhibits an unprecedented 6-nodal net of {4,64,8}4{42,610,83}{42,64}{42,66,82}2 topology. Moreover, compound 1 emits intense luminescence in the solid state at room temperature.Presented here is a new chiral Sr(II) doped Cd(II)-tartrate, which features a two distinct layers and can be described as an unprecedented 6-nodal net of {4,64,8}4{42,610,83}{42,64}{42,66,82}2 topology.Highlights► New chiral Sr(II) doped Cd(II)-tartrate. ► Its structure contains two distinct layers. ► It presents an unprecedented 6-nodal topological net.
Co-reporter:Xin Zhang, Jian-Kai Cheng, Ming-Jian Zhang, Yuan-Gen Yao
Inorganic Chemistry Communications 2012 20() pp: 101-104
Publication Date(Web):
DOI:10.1016/j.inoche.2012.02.027
Co-reporter:Pei-Xiu Yin, Jian Zhang, Ye-Yan Qin, Jian-Kai Cheng, Zhao-Ji Li and Yuan-Gen Yao
CrystEngComm 2011 vol. 13(Issue 10) pp:3536-3544
Publication Date(Web):18 Mar 2011
DOI:10.1039/C0CE00762E
Five members of the Zn/Cd triazolate family, [Zn(TAZ)(OAc)]n (1), [Zn4(TAZ)6(OAc)2]n (2), [Cd3Cl3(TAZ)3(DMF)2]n (3), [CdCl2(TAZ)]n·n(H2O) (4) and [Cd2Cl(μ4-AmTAZ)2(μ-AmTAZ)]n (5), have been synthesized from TAZ/AmTAZ and corresponding metal salts, where TAZ, AmTAZ and DMF are 1,2,4-triazole, 3-amino-1,2,4-triazole and N,N′-dimethylformamide, respectively. X-ray analysis shows that all compounds except 4 manifest interesting 3D frameworks with novel topologies. Compounds 1 and 2 are temperature-and-solvent controlled assemblies and possess 3D (3,4,6)-connected (3.72)2(32.4.73)(32.4.76.86) topology and 3D (3,6)-connected (4.82)3(83)(46.86.123) topology, respectively. However, compounds 3 and 4 are molar-ratio-dependent compounds. The framework of 3 is a 3D (3,4,5)-connected one with (4.102)(4.62)2(43.62.8)2(64.106) topology, in which the 1D channels are filled with coordinated DMF, while only a 1D chain-like motif is formed in 4. In addition, a 3D (4,6)-connected (3.42.52.6)2(32.42.54.65.72)(32.44.54.64.7) topology is observed in the framework of 5, where AmTAZ is used instead of TAZ in the syntheses of compounds 1–4. Solid state measurements reveal that all these coordination polymers are thermostable and luminescent under ambient conditions.
Co-reporter:Xin Zhang, Jin-Xia Yang, Jian Zhang, Jian-Kai Cheng, Ming-Ling Sun, Yuan-Gen Yao
Inorganic Chemistry Communications 2011 Volume 14(Issue 6) pp:986-989
Publication Date(Web):June 2011
DOI:10.1016/j.inoche.2011.03.050
A new compound, namely [Cd3(L1)2(μ2-H2O)2]n·3nH2O (1 H3L1 = 5-(benzonic-4-ylmethoxy)-isophthalic acid), containing one-dimensional (1D) foot-shaped channels was hydrothermally synthesized. It was a three-dimensional pillar-layered framework based on rod-shaped metal-carboxylate second building units (SBUs) and designed T-shaped polycarboxylate ligand. Remarkably, 1D zigzag water chains directed by hydrogen bonds were captured in the channels, further stabilizing the whole framework. Moreover, this compound exhibits strong blue photoluminescence at room temperature.Presented here is a new three dimensional (3D) open Cd(II) coordination polymer, [Cd3(L1)2(μ2-H2O)2]n·3nH2O (1 H3L1 = 5-(benzonic-4-ylmethoxy)-isophthalic acid), which captures a one dimensional (1D) zigzag water chain in the channels and exhibits strong blue photoluminescence at room temperature.Research Highlights► In this work, we designed and synthesized a new semi-rigid T-shaped tricarboxylate ligand,5–(benzonic–4–ylmethoxy)–isophthalic acid (H3L1). ► The hydrothermal reaction of Cd(OAC)2•2H2O with H3L1 lead to a new open cadmium(II) compound. ► One-dimensional zigzag water chains were captured in the foot-shaped channels.
Co-reporter:Xin Zhang, Jiankai Cheng, Feng Chen, Mingling Sun, Yuangen Yao
Inorganic Chemistry Communications 2011 Volume 14(Issue 2) pp:358-361
Publication Date(Web):February 2011
DOI:10.1016/j.inoche.2010.11.032
The hydrothermal reaction of Pb(OAC)2·3H2O with the flexible multidentate ligand 5-(pyridin-2-ylmethoxy)-isophthalic acid (H2L1) or 5-(pyridin-4-ylmethoxy)-isophthalic acid (H2L2), respectively, afforded two new metal–organic frameworks, [Pb2L12]n (1) and [Pb2L22]n (2). The single-crystal X-ray analysis shows that 1 is a two-dimensional (2D) layered structure, whereas 2 is a three-dimensional (3D) pillar-layered network. Both of them exhibit strong yellow photoluminescence upon excitation 366 nm at room temperature.Presented here are two new isomeric photoluminescent Pb(II) coordination polymers, [Pb2L12]n (1, L1 = 5-(pyridin-2-ylmethoxy)-isophthalate) and [Pb2L22]n (2, L2 = 5-(pyridin-4-ylmethoxy)-isophthalate), which possess distinct topological structures and photoluminescent properties.Research Highlights► In this work, we designed and synthesized two new pyridinecarboxylic aids, 5-(pyridin-2-ylmethoxy)-isophthalic acid (H2L1) and 5-(pyridin-4-ylmethoxy)-isophthalic acid (H2L2) (Scheme 1). ► There exists a flexible CH2-O spacer between the pyridine and phenyl ring in both structures of H2L1 and H2L2, which will enable them adopt suitable configurations according to the geometric requirements of different metal ions during the self-assembly process. ► Successfully, the hydrothermal reactions of Pb(OAC)2•3H2O with H2L1 and H2L2, respectively, lead to two novel lead (II) compounds, [Pb2(L1)2]n (1) and [Pb2(L2)2]n (2).
Co-reporter:Ling Lin, Xin Zhang, Jian Zhang, Yuan-Gen Yao
Journal of Molecular Structure 2011 Volume 1006(1–3) pp:83-86
Publication Date(Web):14 December 2011
DOI:10.1016/j.molstruc.2011.07.033
P-4mo-BDCME (5-(pyridine-4-ylmethoxy)-isophthalic acid dimethyl ester) is undergoing hydrolysis, C–O ether bond cleavage and simultaneous self-assembly with Pr(III) to produce a new chiral compound, [Pr2(HO–BDC)3(H2O)2] (1 HO–BDC = 5-hydroisophthalic acid), which features a three-dimensional (3D) framework with right-handed helices. Moreover, the magnetic behavior of 1 was investigated in the temperature range of 2–300 K.
Co-reporter:Lu-Yang Qiao, Jian Zhang, Zhao-Ji Li, Ye-Yan Qin, Pei-Xiu Yin, Jian-Kai Cheng, Yuan-Gen Yao
Journal of Molecular Structure 2011 Volume 994(1–3) pp:1-5
Publication Date(Web):17 May 2011
DOI:10.1016/j.molstruc.2011.02.034
The reactions of Cu(II) sulfate with 4-Amino-1,2,4-triazole (Atrz) and 1,3,5-Benzenetricarboxylic acid (H3BTC) gave a novel interesting coordination polymer {[Cu5(BTC)4(HAtrz)2(H2O)9]}n. The structure contains 2D undulated molecular layers. The BTC side arms can thread through the voids of adjacent polymeric units guided by strong intermolecular hydrogen bonding interactions, exhibiting an unusual 2D → 3D polythreading with finite components.
Co-reporter:Jin-Xia Yang, Xin Zhang, Jian-Kai Cheng, Yuan-Gen Yao
Journal of Molecular Structure 2011 Volume 991(1–3) pp:31-34
Publication Date(Web):5 April 2011
DOI:10.1016/j.molstruc.2011.01.036
A novel Zn(ΙI) complex, [Zn(L1)(bpe)] (1) (H2L1 = 5-(benzyloxy) isophthalic acid, bpe = 1,2-bis(4-pyridyl)ethane) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, IR and X-ray powder diffraction (PXRD). Compoud 1 features a one-dimensional (1D) open-ended tubular framework. These adjacent tubular frameworks are interdigitated into a two-dimensional (2D) supramolecular framework directed by hydrogen bonds. Moreover, this compound exhibits intense blue photoluminescence at room temperature.
Co-reporter:Pengbin Pan, Chuan-Fu Sun, Shu-Mei Chen, Yuangen Yao
Inorganic Chemistry Communications 2011 Volume 14(Issue 9) pp:1333-1336
Publication Date(Web):September 2011
DOI:10.1016/j.inoche.2011.05.007
Two new Cd(II)-tetrazole coordination polymers with different auxiliary anions, namely [Cd10(ATZ)13(ac)2(H2O)2F5]•2H2O (1) and [Cd3(ATZ)4Cl2(C2H5OH)2] (2), were solvothermally synthesized and structurally characterized. Both compounds exhibit interesting three-dimensional Cd-ATZ frameworks, but their coordination networks are totally different and show distinct topologies.Two new Cd-ATZ frameworks with different auxiliary anions exhibit distinct 12-nodal (3,4,5)-connected topology and 3-nodal (3,4)-connected topology, respectively.Research highlights► New Cd(II)-tetrazole coordination polymers with different auxiliary anions. ► Three-dimensional Cd-ATZ frameworks with distinct topologies. ► Anion-controlled versatility of coordination frameworks.
Co-reporter:Xin Zhang, Jian-Kai Cheng, Pei-Xiu Yin, Yuan-Gen Yao
Journal of Molecular Structure 2011 990(1–3) pp: 1-5
Publication Date(Web):29 March 2011
DOI:10.1016/j.molstruc.2010.10.039
A novel coordination polymer, [Pb4(L1)3(μ4-O)(H2O)]n (1 H2L1 = 5-(pyridine-2-ylmethoxy)-isophthalic acid), was hydrothermally synthesized, which contains μ4-oxygen-bridged Pb4O tetrahedral clusters as building subunits. These isolated Pb4O tetrahedral clusters are combined by the L1 ligands, extending into a two-dimensional (2D) layered motif. Finally, these parallel layers are further linked by intermolecular CH⋯π interactions to form a three-dimensional (3D) stacked supramolecular architecture. Moreover, this polymer exhibits strong photoluminescence at room temperature.
Co-reporter:Ming-Ling Sun ; Jian Zhang ; Qi-Pu Lin ; Pei-Xiu Yin
Inorganic Chemistry 2010 Volume 49(Issue 20) pp:9257-9264
Publication Date(Web):September 16, 2010
DOI:10.1021/ic1007445
Seven homochiral lanthanide camphorates with mixed achiral terephthalate ligands, namely, {Ln2(cam)2(bdc)(H2O)2}·DMF [Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5), Ho (6), Er (7); d-H2cam = d-(+)-camphoric acid; H2bdc = 1,4-benzenedicarboxylic acid; DMF = N,N′-dimethylformamide], have been solvothermally synthesized. Single-crystal X-ray diffraction analyses reveal that compounds 1−7 are isostructural and crystallize in orthorhombic, chiral space group P212121. These structures feature three-dimensional open frameworks based on rodlike [Ln2(OCO)6(H2O)2]n secondary building units, with the guest DMF molecules occupying the void space of the host {Ln2(cam)3(bdc)(H2O)2} framework. The photophysical and magnetic properties of some of these complexes have been investigated. Notably, the terbium compound 4 is highly emissive with a quantum yield of 63.68%. Additionally, thermogravimetric analyses, variable-temperature IR spectrscopy, and powder X-ray diffraction of 2 as a representative were performed to determine its thermal stability, which indicates that the framework still remains intact until 300 °C.
Co-reporter:Ming-Ling Sun, Lei Zhang, Qi-Pu Lin, Jian Zhang and Yuan-Gen Yao
Crystal Growth & Design 2010 Volume 10(Issue 4) pp:1464-1467
Publication Date(Web):February 18, 2010
DOI:10.1021/cg901468d
Presented here is an unusual visible concentration-sensitive structural transformation between two supramolecular compounds; such a complete and reversible process is accompanied by dramatic ligand exchange and framework rebuilding in a single crystal.
Co-reporter:Qi-Pu Lin, Jian Zhang, Xin-Yi Cao, Yuan-Gen Yao, Zhao-Ji Li, Lei Zhang and Zhang-Feng Zhou
CrystEngComm 2010 vol. 12(Issue 10) pp:2938-2942
Publication Date(Web):12 May 2010
DOI:10.1039/B923235D
The hydrothermal reaction of the versatile ligand 5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7(4H)-one (Hmtpo), and cobalt/nickel acetate afforded two isostructural Co(II) and Ni(II) frameworks [M(mtpo)2(H2O)]n (M = Co (1Co) or Ni (2Ni)). Both of them consist of heterochiral helical meshes fused together into a non-interpenetrated lvt topological network containing only planar four-coordinate nodes. The frameworks can be rationalized to a rare 6-c crs net if the water-donated hydrogen-bonds are considered. Two isomorphous complexes exhibit spin-canted antiferromagnetism, with the critical temperature Tc of ca. 3.0 K for 1Co and 19 K for 2Ni. The additional magnetic measurements (after the removal of guest molecules), IR, TGA and XRPD of the complexes were also discussed.
Co-reporter:Jian-Kai Cheng, Jian Zhang, Pei-Xiu Yin, Qi-Pu Lin, Zhao-Ji Li and Yuan-Gen Yao
CrystEngComm 2010 vol. 12(Issue 4) pp:1024-1026
Publication Date(Web):05 Nov 2009
DOI:10.1039/B916206B
An unprecedented in situ generated NHCH–NNH molecule successfully templated the formation of a photoluminescent 4-connected open Cd(II) framework with the umc topology, which first demonstrated the ring-opening reaction from the N,S-containing ligand. The results provide a new templating synthetic route to understand the mechanism of hydro(solvo)thermal in situ ligand synthesis via capturing small in situ generated molecular fragments.
Co-reporter:Pei-Xiu Yin ; Jian-Kai Cheng ; Zhao-Ji Li ; Lei Zhang ; Ye-Yan Qin ; Jian Zhang
Inorganic Chemistry 2009 Volume 48(Issue 23) pp:10859-10861
Publication Date(Web):November 4, 2009
DOI:10.1021/ic9007813
Ag(I)-mediated in situ generation of 3,3′-azobis(1,2,4-triazole) (AzTAZ) from 3-amino-1,2,4-triazole (AmTAZ) through dehydrogenative coupling has been realized during the crystallization process of two Cd(II) coordination polymers with novel topological architectures: a (3, 4, 5)-connected (4·62)2(4·67·82)2(65·10) net for [Cd2(AmTAZ)2(AzTAZ)]n (1) and a 4-connected (62·84)(64·82)(65·8)2 net for [Cd(AzTAZ)2(H2O)]n (2), whereas AmTAZ retains its original form in a heterometallic complex, [Ag2Cd(AmTAZ)4]n (3).
Co-reporter:Lei Zhang, Zhao-Ji Li, Qi-Pu Lin, Ye-Yan Qin, Jian Zhang, Pei-Xiu Yin, Jian-Kai Cheng and Yuan-Gen Yao
Inorganic Chemistry 2009 Volume 48(Issue 14) pp:6517-6525
Publication Date(Web):June 15, 2009
DOI:10.1021/ic900425r
The hydro(solvo)thermal reactions of Pb(OAc)2·3H2O with the aromatic carboxylic ligands 1,3,5-benzenetricarboxylic and 1,4-, 1,2-, and 1,3-benzenedicarboxylic acids (1,3,5-H3BTC; 1,4-, 1,2-, and 1,3-H2BDC) have yielded a family of inorganic−organic framework materials: [Pb2(1,3,5-BTC)(μ3-OH)(H2O)]n (Ι), [NaPb(1,3,5-BTC)(H2O)]n (ΙΙ), [Pb(1,4-BDC)]n (ΙΙΙ), [Pb5(1,2-BDC)4(OAc)2]n (IV), and {[Pb5(1,3-BDC)5(H2O)2]2·H2O}n (V). These complexes have been characterized by means of single-crystal X-ray diffraction, X-ray powder diffraction, thermogravimetric analysis−mass spectrometry, and photoluminescence spectra. They are all three-dimensional structures except for two-dimensional IV. Topology analysis reveals that complexes I an V represent rare (4,8)-connected flu and (3,4)-connected zeolite-like nets, respectively. The five complexes exhibit diverse inorganic connectivity, including a 0D Pb4O16 cluster for I, a 1D Pb−O−Pb chain for II, a 2D Pb−O−Pb network for III and IV, and an unprecedented 3D Pb−O−Pb framework for V. And the diversity in inorganic arrays leads to differences in luminescent properties of these complexes.
Co-reporter:Jian-Kai Cheng, Jian Zhang, Pei-Xiu Yin, Qi-Pu Lin, Zhao-Ji Li and Yuan-Gen Yao
Inorganic Chemistry 2009 Volume 48(Issue 21) pp:9992-9994
Publication Date(Web):October 6, 2009
DOI:10.1021/ic901653y
Three isomorphous lead(II) complexes with a new {N3SX}-coordinated (X = Cl, Br, I) mode have been synthesized and characterized by X-ray diffraction. The structural analyses reveal that the coordination environment around the center metal is distinctly influenced by the stereochemical 6s2 lone pair and N−H···X hydrogen bonds. Additionally, doubly deprotonated trzS2− (HtrzSH = 1,2,4-triazole-3-thiol) generated in situ via deamination and dehydrazination of ahtrzS− (ahtrzSH = 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole) was first observed in a semiconducting three-dimensional coordination network at higher reaction temperature.
Co-reporter:Lei Zhang, Zhao-Ji Li, Qi-Pu Lin, Jian Zhang, Pei-Xiu Yin, Ye-Yan Qin, Jian-Kai Cheng and Yuan-Gen Yao
CrystEngComm 2009 vol. 11(Issue 9) pp:1934-1939
Publication Date(Web):28 May 2009
DOI:10.1039/B905794C
Two novel coordination polymers, {[Cu2(THFTCA)(phen)] · H2O}n (1) and [Cd2(THFTCA)(H2O)3]n (2) (H4THFTCA = (2S,3S,4R,5R)-tetrahydrofurantetracarboxylic acid, phen = 1,10-phenanthroline), have been prepared under hydro(solvo)thermal conditions and characterized by X-ray diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis reveals that both complexes 1 and 2 crystallize in the P21/c space group. The structure of complex 1 is based on 2D (3,6)-connected kgd-type (43)2(46.66.83) layers, which are further extended into a 3D supramolecular architecture through π–π packing interactions of phen. Complex 2 is the first reported Cd-tetrahydrofurantetracarboxylate and represents a complicated 3D metal–organic framework (MOF) structure with (4,6)-connected (44.62)(46.69) topology. The configurations of THFTCA ligands in the two complexes are all meso-(2S,3S,4R,5R) form. The luminescent properties of 2 have also been investigated.
Co-reporter:Xin-Yi Cao, Yuan-Gen Yao, Ye-Yan Qin, Qi-Pu Lin, Zhao-Ji Li, Jian-Kai Cheng and Rui-Bo Zhang
CrystEngComm 2009 vol. 11(Issue 9) pp:1815-1818
Publication Date(Web):02 Jun 2009
DOI:10.1039/B904387J
Various decomposition products of C–O ether bond cleavage have been trapped in supramolecular architectures as templates based on hydrothermal reaction of three-component metal–carboxylate–phen, which not only results in the formation of [5]pseudorotaxane structure, 3D porous framework and supramolecular structure, but also provides directly crystallographic evidence to explain how the C–O ether bond breaks during decomposition.
Co-reporter:Lei Zhang, Qi-Pu Lin, Zhao-Ji Li, Jian Zhang, Ye-Yan Qin, Jian-Kai Cheng and Yuan-Gen Yao
CrystEngComm 2009 vol. 11(Issue 7) pp:1201-1203
Publication Date(Web):07 Apr 2009
DOI:10.1039/B822767E
Two supramolecular structures have been prepared using flexible (2S,3S,4R,5R)-tetrahydrofurantetracarboxylic acid (H4Laa) and cis,cis,cis-1,2,3,4-cyclopentanetetracarboxylic acid (H4Lbb) under similar conditions; Laa retains its original meso configuration, while Lbb undergoes configuration conversion to the racemic form.
Co-reporter:Xin-Yi Cao, Yuan-Gen Yao, Stuart R. Batten, En Ma, Ye-Yan Qin, Jian Zhang, Rui-Bo Zhang and Jian-Kai Cheng
CrystEngComm 2009 vol. 11(Issue 6) pp:1030-1036
Publication Date(Web):07 Feb 2009
DOI:10.1039/B820600G
Three novel luminescent metal–organic frameworks [Zn(1,2-BBOMB)(4,4′-bipy)1/2]n (1), [Zn2(1,3-BBOMB)2(4,4′-bipy)]n (2) and [Zn4(1,2-BBOMB)4(bpp)2]n (3) have been synthesized by combining the conformationally flexible V-shaped long multicarboxylate ligands and the rigid 4,4′-bipy or flexible bpp ligands with zinc ions under hydrothermal conditions. It is worth mentioning that the layers observed in the three compounds can be reduced to the same 6-connected topological net with (22·48·65) symbol. These complexes display a structural evolution from a two-dimensional (2D) polyrotaxane and polycatenane framework to a three-dimensional (3D) architecture with coexistence of polyrotaxane, polycatenane and interdigitation. The three species contain loops and rods that are interlaced in a highly rare parallel fashion, but with twofold (2D → 2D), triply (2D → 2D) and triply (2D → 3D) entangled features in complexes 1, 2 and 3, respectively. Furthermore, the rotaxane-like interactions between the loops and the rods exhibit a progressive change from one loop interacting with a single rod, to one loop interacting with two identical rods, to finally one loop interacting with two conformationally different rods in complexes 1, 2 and 3, respectively. Photoluminescence studies revealed that these complexes are potential violet, blue and green luminescent materials. The thermal stabilities of these complexes were also discussed.
Co-reporter:Xin-Yi Cao, Qi-Pu Lin, Ye-Yan Qin, Jian Zhang, Zhao-Ji Li, Jian-Kai Cheng and Yuan-Gen Yao
Crystal Growth & Design 2009 Volume 9(Issue 1) pp:20
Publication Date(Web):December 8, 2008
DOI:10.1021/cg800938y
The present study describes the preparation and characterization of the first example of metal−organic frameworks (MOFs) with the coexistence of polycatenation and polythreading involving chemically and structurally different two-dimensional square grids [Cu(II)2(5-HIPA)2(4,4′-bipy)2(H2O)2]n (A, 5-HIPA = 5-hydroxyisophthalato) and irregular layers [Cu(II)3(5-HIPA)2(2-PyC)2(4,4′-bipy)2(H2O)4]n (B) in a unique three-dimensional framework [(A)(B)]·6.5nH2O (1) with the in situ generated pyridine-2-carboxylate (2-PyC) ligand.
Co-reporter:Pei-Xiu Yin, Jian Zhang, Zhao-Ji Li, Ye-Yan Qin, Jian-Kai Cheng, Lei Zhang, Qi-Pu Lin and Yuan-Gen Yao
Crystal Growth & Design 2009 Volume 9(Issue 11) pp:4884
Publication Date(Web):August 27, 2009
DOI:10.1021/cg9006839
A systematic investigation on the Ag/bpy/(H)dpa family represents seven Ag(I) supramolecular compounds with distinct structural features, Ag2(bpy)0.5(dpa) (1), Ag2(bpy)1.5(dpa)(H2O) (2), Ag(bpy)0.5(Hdpa) (3), α-[Ag(bpy)]·(Hdpa) (4), β-[Ag(bpy)]·(Hdpa) (5), [Ag(bpy)]2·(dpa)·6(H2O) (6), and [Ag(bpy)]4·(dpa)·2(NO3)·6(H2O) (7) (H2dpa = 1,1′-biphenyl-2,2′-dicarboxylic acid, bpy = 4,4′-bipyridine). Of particular interest about this work is that supramolecular isomerism is observed between compounds 4 and 5. Single-crystal X-ray structural analysis reveals the structural diversity of the formed products. Compounds 1−5 are extended from various one-dimensional (1D) chain substructures. Three distinct 1D chains exist in 1−3: one 1D chain of {Ag2(dpa)} exists in compound 1, one supramolecular chain of tetranuclear {Ag2(dpa)(H2O)}2 subunits linked by Ag···Ag interactions (argentophilic interactions) and hydrogen bonding interactions is observed in 2, and one 1D alternate chain of eight-membered {Ag2(Hdpa)2} ring bridged by bpy is present in 3. However, two different 1D supramolecular double chains of [Ag(bpy)(Hdpa)] are found in 4 and 5, which are sustained by the combination of weak Ag···O interactions, π−π stacking interactions, and argentophilic interactions in 4 while only by π−π stacking interactions in 5. These 1D chain substructures are further threaded into a 2D covalent layer bridged by bpy (1) or 2D (3 and 4)/3D (2 and 5) supramolecular architectures with the help of supramolecular driving forces in different ways. In contrast to compounds 1−5, compounds 6 and 7 are based upon 2D supramolecular substructures of [Ag(bpy)]2·(dpa) and {[Ag(bpy)]4·(dpa)·(H2O)}n2n+, respectively. The most striking feature of 6 is that a quasi-1D water aggregate is confined in the 1D channel of the 3D porous interdigitated host framework. Greatly different from compound 6, compound 7 is a nitrate-templated 3D supramolecular framework constructed from a positively charged layer substructure through versatile hydrogen bonds. The diversity of the product structures illustrates that controlled synthesis by adjusting the molar ratio of precursors or the pH value of the solution is a facile and effective approach to further design and construct novel supramolecular assemblies with distinct structural features. Moreover, the thermal dynamic properties and fluorescent properties of all compounds except 1 are also investigated.
Co-reporter:Lei Zhang;Jian Zhang Dr.;Zhao-Ji Li ;Ye-Yan Qin;Qi-Pu Lin Dr.
Chemistry - A European Journal 2009 Volume 15( Issue 4) pp:989-1000
Publication Date(Web):
DOI:10.1002/chem.200801948
Abstract
To study the conversion from a meso form to a racemic form of tetrahydrofurantetracarboxylic acid (H4L), seven novel coordination polymers were synthesized by the hydrothermal reaction of Zn(NO3)2⋅6 H2O with (2S,3S,4R,5R)-H4L in the presence of 1,10-phenanthroline (phen), 2,2′-bipyridine (2,2′-bpy), or 4,4′-bipyridine (4,4′-bpy): [Zn2{(2S,3S,4R,5R)-L}(phen)2(H2O)]⋅2 H2O (1), [Zn4{(2S,3R,4R,5R)-L}{(2S,3S,4S,5R)-L}(phen)2(H2O)2] (2), [Zn2{(2S,3S,4R,5R)-L}(H2O)2]⋅H2O (3), [Zn4{(2S,3R,4R,5R)-L}{(2S,3S,4S,5R)-L} (2,2′-bpy)2(H2O)2]⋅2 H2O (4), [Zn2 {(2S,3S,4R,5R)-L}(2,2′-bpy)(H2O)] (5), [Zn4{(2S,3R,4R,5R)-L}{(2S,3S,4S,5R)-L} (4,4′-bpy)2(H2O)2] (6), and [Zn2 {(2S,3S,4R,5R)-L}(4,4′-bpy)(H2O)]⋅ 2 H2O (7). These complexes were obtained by control of the pH values of reaction mixtures, with an initial of pH 2.0 for 1, 2.5 for 2, 4, and 6, and 4.5 for 3, 5, and 7, respectively. The expected configuration conversion has been successfully realized during the formation of 2, 4, and 6, and the enantiomers of L, (2S,3R,4R,5R)-L and (2S,3S,4S,5R)-L, are trapped in them, whereas L ligands in the other four complexes retain the original meso form, which indicates that such a conversion is possibly pH controlled. Acid-catalyzed enol–keto tautomerism has been introduced to explain the mechanism of this conversion. Complex 1 features a simple 1D metal–L chain that is extended into a 3D supramolecular structure by π–π packing interactions between phen ligands and hydrogen bonds. Complex 2 has 2D racemic layers that consist of centrosymmetric bimetallic units, and a final 3D supramolecular framework is formed by the interlinking of these layers through π–π packing interactions of phen. Complex 3 is a 3D metal–organic framework (MOF) involving meso-L ligands, which can be regarded as (4,6)-connected nets with vertex symbol (45.6)(47.68). Complexes 4 and 5 contain 2D racemic layers and (6,3)-honeycomb layers, respectively, both of which are combined into 3D supramolecular structures through π–π packing interactions of 2,2′-bpy. The structure of complex 6 is a 2D network formed by 4,4′-bpy bridging 1D tubes, which consist of metal atoms and enantiomers of L. These layers are connected through hydrogen bonds to give the final 3D porous supramolecular framework of 6. Complex 7 is a 3D MOF with novel (3,4,5)-connected (63)(42.64)(42.66.82) topology. The thermal stability of these compounds was also investigated.
Co-reporter:Rui-Bo Zhang, Jian Zhang, Zhao-Ji Li, Ye-Yan Qin, Jian-Kai Cheng and Yuan-Gen Yao
Chemical Communications 2008 (Issue 35) pp:4159-4161
Publication Date(Web):15 Jul 2008
DOI:10.1039/B807320A
Luminescent acentric and homochiral coordination compounds, which possess new topological networks, multiple helical structures and NLO properties, have been generated through the control of a versatile asymmetric ligand as well as inorganic anions, and this suggests a new protocol for preparing acentric and chiral materials.
Co-reporter:Ye-Yan Qin, Jian Zhang, Zhao-Ji Li, Lei Zhang, Xin-Yi Cao and Yuan-Gen Yao
Chemical Communications 2008 (Issue 22) pp:2532-2534
Publication Date(Web):28 Mar 2008
DOI:10.1039/B800017D
A new organic cation templated Zn(II) complex (Et3NH)[Zn4(ip)3(bta)3] (1, ip = isophthalate, Hbta = benzotriazole) which consists of plate-like Zn4(bta)3 units bridged by ip ligands is reported; it is the first example of a 6-connected uninodal {33.59.63}-lcy net which has never been observed previously in MOFs but has been theoretically anticipated.
Co-reporter:Rui-Bo Zhang ; Zhao-Ji Li ; Ye-Yan Qin ; Jian-Kai Cheng ; Jian Zhang
Inorganic Chemistry 2008 Volume 47(Issue 11) pp:4861-4876
Publication Date(Web):May 2, 2008
DOI:10.1021/ic8001042
Nine members of a new anions-controlled Cd(II)-guanazole (3,5-diamino-1,2,4-triazole = Hdatrz ) hybrid family, that is, [Cd3(datrz)6(H2O)2] (1), [Cd3(datrz)4F2] (2), [Cd5(datrz)4Cl4(OH)2] (3), [Cd5(datrz)4Br4(OH)2] (4), [Cd3(datrz)2(SO3)2]·(H2O) (5), [Cd3(datrz)2(O2CMe)4] (6), [Cd(datrz)(O2CEt)] (7), [Cd(Hdatrz)(O2CtBu)2] (8), and [Cd(Hdatrz)2(H2Edta)] (9) have been synthesized by exploiting hydrothermal reactions of guanazole with suitable cadmium salts under appropriate reaction conditions. With effective control of inorganic or organic anions, the coordination diversity of the guanazole ligand in 1−9 manifests an unprecedented enrichment with five bridging modes varying from bidentate to quadridentate, two of which are first reported. Compound 1 is the first reported three-dimensional chiral complex constructed from the guanazole ligand which adopts a novel N1, N2, amino N-bridging mode. Halogen anions F−, Cl−, and Br− controlled compounds 2−4 are all three-dimensional, with their guanazole ligands possessing another novel quadridentate bridging mode. Sulfite anions controlled compound 5 displays a three-dimensional network with peculiar cage-like hexnuclear cadmium clusters. As for organic anions, low dimensional structures have been found for alkylcarboxylate anions MeCO2−, EtCO2−, and tBuCO2− controlled compounds 6, 7, and 8 (two-dimensional) and for H2Edta2− controlled compound 9 (zero- dimensional), and their guanazole ligands manifest low coordination numbers as well. These hybrid materials also present interesting structure-induced physical properties. The chiral compound 1 exhibits the second-order nonlinear optical properties at room temperature. Compounds 2−9 except 6 all exhibit photoluminescence of blue fluorescent emissions in the solid state at ambient temperature, which may be assigned to the intraligand π−π* transitions. Some structure related red or blue emission shifts have been investigated. Thermal studies show that most compounds of this study possess a high thermal stability.
Co-reporter:Lei Zhang ; Ye-Yan Qin ; Zhao-Ji Li ; Qi-Pu Lin ; Jian-Kai Cheng ; Jian Zhang
Inorganic Chemistry 2008 Volume 47(Issue 18) pp:8286-8293
Publication Date(Web):August 16, 2008
DOI:10.1021/ic800871r
Two 3D Zn(II) and Pb(II) isophthalates, [Zn(ip)]n (1) and [Pb4(μ4-O)(ip)3(H2O)]n (2) (H2ip = isophthalic acid), have been prepared under hydro(solvo)thermal conditions and characterized by single-crystal X-ray diffraction. The two complexes crystallize in different space groups (P43212 for 1 and P21/c for 2) and have different bridging modes of the ip ligand. The 3D framework of 1 is constructed by the interconnection of ZnO4 polyhedra via ip ligands, which represents a chiral net with PtS-type topology. In contrast, complex 2 is formed by the combination of Pb4O-cluster secondary building units and has a novel (3.4.5)(32.45.56.67.72) topology, which is the first ever example of a (3,7)-connected net. Complex 1 displays a second harmonic generation efficiency of about 1.5 times that of KH2PO4. Optical properties and thermal stabilities of the two complexes have been studied. Additionally, the calculations of band structure and density of states of 1 have also been performed with the density functional theory method.
Co-reporter:Rui-Bo Zhang, Zhao-Ji Li, Jian-Kai Cheng, Ye-Yan Qin, Jian Zhang and Yuan-Gen Yao
Crystal Growth & Design 2008 Volume 8(Issue 7) pp:2562-2573
Publication Date(Web):June 3, 2008
DOI:10.1021/cg800199x
A new hybrid system of cadmium(II) polymers has been synthesized by using 1H-1,2,4-triazole-3-thiol (HtrzSH) and cadmium salts, affording six novel luminescent complexes, that is, [Cd(H2trzS)2Cl2] (1), [Cd(HtrzS)Br] (2), [Cd(HtrzS)I] (3), [Cd2(HtrzS)2(SO4)] (4), [Cd(H2trzS)(H2Edta)]·(H2O) (5), and [Cd(trzS)2] (6). In these materials, owing to the effective inducement of inorganic or organic anions, coordination versatility of the HtrzSH ligand manifests as many as six bridging modes (type A−F), and five of them (type B−F) are first reported. The structure of complex 1 is a one-dimensional chain constructed from the neutral monodentate and bidentate H2trzS ligand (type A−B), whereas two-dimensional complexes 2−3 and the three-dimensional complex 4 possess the deprotonated tridentate to quadridentate HtrzS ligands (type C−E). Zero-dimensional complex 5 and peristyle-like three-dimensional complex 6 are synthesized by means of organic anions, and in the latter complex a bideprotonated quadridentate trzS ligand is presented (type F). All complexes exhibit strong photoluminescence with fluorescent emissions varying from blue to orange in the solid state. Some structure related red or blue emission shifts compared to the free ligand are studied, as well as several advantageous structural factors to obtain longer fluorescence lifetime. X-ray powder diffraction and thermal studies are used to investigate the bulk properties of these compounds.
Co-reporter:Rui-Bo Zhang, Jian Zhang, Zhao-Ji Li, Jian-Kai Cheng, Ye-Yan Qin and Yuan-Gen Yao
Crystal Growth & Design 2008 Volume 8(Issue 10) pp:3735-3744
Publication Date(Web):August 29, 2008
DOI:10.1021/cg800378c
Hydrothermal reactions of copper(I) or copper(II) salts with guanazole (3,5-diamino-1,2,4-triazole = Hdatrz) have yielded three novel 3D Cu-guanazolate complexes, that is, [Cu7Br6][Cu(datrz)2] (1), [Cu(datrz)] (2), and [Cu4(datrz)2(OH)2(SO4)2] (3). Complex 1 presents the first example in Cu(I) halide complexes with its Cu(I) bromide units {Cu7Br6}nn+ adopting a 3D network, which is constructed from two unprecedented substructures: the edge-sharing eight-membered {Cu4Br4}n rings and the three-bladed paddle-wheel-like {Cu4Br4}n units. Guanazolate ligands in 1 adopt an unprecedented pentadentate bridging mode and some bromide ligands exhibit a rare umbrella-like μ4 coordination geometry. The first binary Cu(I) guanazolate 2 exhibits a seldom reported two-fold interpenetrated lvt-a net, which can be partially controlled through the fixing effect of inter-ligand hydrogen bonds. Cu(II) complex 3 comprises a rarely encountered 12-connected tetranuclear {Cu4(μ3-OH)2} SBU, which is bridged by guanazolate ligands adopting a peculiar quadridentate coordination mode. This complex displays a non-interpenetrated pcu net, which is first constructed from multinuclear Cu(II) SBUs. Both 1 and 2 exhibit strong, broad, and unstructured emissions with long luminescence lifetimes, which may be assigned to the 3[MLCT] ES, and the 3[MC] or 3[MMLCT] ES could also be possible for 1. Complex 3 exhibits magnetic properties with four Cu(II) centers antiferromagnetically coupled in a tetranuclear array, which enables multiple and strong exchange interactions of J1 = −95.1, J2 = −152.7, and J3 = −55.4 cm−1. All compounds of this study display a medium to high thermal stability, and complex 1 shows the highest one with its structure framework unchanged up to 540 °C. Some significant structure−function correlations are discussed in this study as well.
Co-reporter:Lei Zhang, Wei Li, Jian Zhang, Zhao-Ji Li, Ye-Yan Qin, Jian-Kai Cheng, Yuan-Gen Yao
Inorganic Chemistry Communications 2008 Volume 11(Issue 3) pp:279-282
Publication Date(Web):March 2008
DOI:10.1016/j.inoche.2007.12.016
The hydrothermal assembly of Co(OAc)2 · 4H2O with isophthalatic acid (H2ip) and melamine (ma) yielded a novel 3D coordination polymeric complex, {[Co3(ma)(ip)3] · 2H2O}n (1), which presents an unusual non-interpenetrated pseudo-primitive cubic (pcu) topology constructed from a 6-connected trinuclear Co(II) SBU. The study of magnetic properties indicates that antiferromagnetic coupling interactions exist both between the adjacent Co(II) sites and between the adjacent trimers. So the melamine molecule participates in transferring magnetic interactions for the first time.A new cobalt trimer complex, [Co3(ma)(ip)3] · 2H2O, has been synthesized hydrothermally and structurally characterized, which exhibits an interesting non-interpenetrated pseudo-pcu metal-organic 3D architecture constructed from a 6-connected SBU. The study of magnetic properties indicated that dominant antiferromagnetic coupling interactions exist between the adjacent Co(II) sites and between the adjacent trimers. And melamine molecule participates in transferring magnetic interactions for the first time.
Co-reporter:Lei Zhang, Zhao-Ji Li, Ye-Yan Qin, Jian Zhang, Jian-Kai Cheng, Pei-Xiu Yin, Yuan-Gen Yao
Journal of Molecular Structure 2008 Volume 891(1–3) pp:138-142
Publication Date(Web):26 November 2008
DOI:10.1016/j.molstruc.2008.03.015
Two novel copper(II) complexes Cu(Hip)2(H2O)2 (1) (H2ip = isophthalic acid) and Cu3(ipO)2(H2O)3 (2) (H3ipO = 2-hydroxy isophthalic acid) have been synthesized through hydrothermal reaction of copper(II) chloride, isophthalic acid, melamine and sodium hydroxide under different pH conditions. The diverse poduct structures show that the pH value of the reaction plays a key role in the hydroxylation of isophthalic acid. The single-crystal X-ray diffraction studies reveal that complex 1 features a 3D supramolecular framework constructed by hydrogen bonds connecting neutral subunits Cu2(Hip)4(H2O)4; whereas complex 2 is based on hexametallic macrocylic building blocks, which are further extended into 2D network through hydrogen-bonding interactions.
Co-reporter:Pei-Xiu Yin, Jian Zhang, Zhao-Ji Li, Ye-Yan Qin, Jian-Kai Cheng, Yuan-Gen Yao
Inorganic Chemistry Communications 2008 Volume 11(Issue 2) pp:134-137
Publication Date(Web):February 2008
DOI:10.1016/j.inoche.2007.11.010
A new zinc compound, [Zn3(DPA)2(BDC)]n (1, H2DPA = diphenic acid and H2BDC = benzene-1,4-dicarboxylic acid), has been hydrothermally prepared and characterized. It illustrates an unusual three-dimensional architecture containing two organic aromatic bicarboxylate ligands with distinct configurations. Moreover, this polymer exhibits strong photoluminescence at room temperature, and the main emission band is at about 390 nm with λex = 337 nm in the solid state at room temperature.A new zinc compound, [Zn3(DPA)2(BDC)]n (1, H2DPA = diphenic acid and H2BDC = benzene-1,4-dicarboxylic acid), has been hydrothermally prepared and characterized. It illustrates an unusual three-dimensional architecture containing two organic aromatic bicarboxylate ligands with distinct configurations. Moreover, this polymer exhibits strong photoluminescence at room temperature, and the main emission band is at about 390 nm with λex = 337 nm in the solid state at room temperature.
Co-reporter:Lan-Fen Chen, Xin-Yi Cao, Zhao-Ji Li, Jian-Kai Cheng, Qi-Pu Lin, Yuan-Gen Yao
Inorganic Chemistry Communications 2008 Volume 11(Issue 9) pp:961-964
Publication Date(Web):September 2008
DOI:10.1016/j.inoche.2008.05.011
A Cu(II)-catalyzed oxidative substitution of pyrazole-3,5-dicarboxylic acid (H3pdc) C–H bonds by bromo/iodo nucleophiles in a self-assembly process under hydrothermal conditions afforded the first halogenated pyrazolecarboxylato-based linear trinuclear copper(II) coordination complexes.A Cu(II)-catalyzed oxidative substitution of pyrazole-3,5-dicarboxylic acid (H3pdc) C–H bonds by bromo/iodo nucleophiles in a self-assembly process under hydrothermal conditions afforded the first halogenated pyrazolecarboxylato-based linear trinuclear copper(II) coordination complexes.
Co-reporter:Hong-Mei Shen, Jian Zhang, Pei-Xiu Yin, Zhao-Ji Li, Zong-Wei Cai, Yuan-Gen Yao
Journal of Molecular Structure 2007 Volume 826(2–3) pp:126-130
Publication Date(Web):29 January 2007
DOI:10.1016/j.molstruc.2006.04.044
The hydrothermal reaction of CdBr2 · 2H2O with a flexible multicarboxylate ligand, trans-aconitic acid (H3L), produced a novel coordination compound [Cd3L2(H2O)6]n. It crystallizes in the space group C2/c with a = 17.1304(1) Å, b = 9.5611(2) Å, c = 14.0137(2) Å, β = 115.96°, Z = 4, V = 2063.65(5) Å3. The unique feature of the structure is an unprecedented 3D framework containing infinite Cd(1)–O–C linear chains and heterochiral Cd(2)–O–C single-stranded helices. These linear chains and helices happen to be perpendicular to each other.
Co-reporter:Pei-Xiu Yin, Jian Zhang, Zhao-Ji Li, Jian-Kai Cheng, Ye-Yan Qin, Lei Zhang, Yuan-Gen Yao
Inorganica Chimica Acta 2007 Volume 360(Issue 11) pp:3525-3532
Publication Date(Web):1 August 2007
DOI:10.1016/j.ica.2007.04.035
Although the 2,2′-biphenyldicarboxylate ligand (2,2′-dpa) has been widely used to construct metal-organic frameworks (MOFs) with helical sub-structure, the effect of the helical arrangement of spin carriers on the magnetic properties remains rarely scarce. In this article, two unique magnetic metal-organic supramolecular frameworks with different structural features, [Cu2(dpa)2(H2O)2(4,4′-dpdo)0.5]n (1) and [Ni(H2O)4(dpa)] · (4,4′-dpdo)(H2O) (2) (dpdo = 4,4′-dipyridine-N,N′-dioxide), have been isolated from the direct reaction of H2dpa with their corresponding salts in the presence of dpdo. In complex 1, the Cu–dpa double-helical chains, which are bridged by long flexible μ2-dpdo ligands to give rise to a regular 63 covalent layer, exhibit strong antiferromagnetic coupling interactions. Whereas the 1D [Ni(dpa)]n helical chains in complex 2 exhibit weak antiferromagnetic coupling interactions. Rich hydrogen bonds between perpendicular 1D [Ni(dpa)]n helical chains and quasi-1D (dpdo)n chains result in an intricate 3D supramolecular network.Two complexes of 2,2′-biphenyldicarboxylate (2,2′-dpa) with helical sub-structure have been synthesized. When the center metal ion is changed from Cu(II) to Ni(II), the structure is then changed from the double stranded helix to the single one, and the strong antiferromagnetic coupling interactions is then changed to weak one.
Co-reporter:Yao Kang, Jian Zhang, Zhao-Ji Li, Jian-Kai Cheng, Yuan-Gen Yao
Inorganica Chimica Acta 2006 Volume 359(Issue 7) pp:2201-2209
Publication Date(Web):25 April 2006
DOI:10.1016/j.ica.2006.02.018
Four MII quinolinato complexes, [Zn2(quin)2(H2O)3]n (1), [Zn(quin)(H2O)2]n (2), [Zn(quin)(H2O)]n (3) and [Cd(quin)]n (4) (H2quin = 2,3-pyridinedicarboxylic acid or quinolinic acid), have been hydrothermally synthesized and structurally characterized. X-ray diffraction analyses reveal that all of these four complexes are constructed from similar rod-like SBUs, [M(quin)]n (M = Zn or Cd). Complexes 1 and 2 have similar 1-D box-like chains but different packing structures; complex 3 has a 2-D grid-like network and complex 4 has an unusual 2-D bilayer structure. Due to the different structural features, these complexes exhibit different photoluminescent emissions: complex 1 at 439 nm (λex = 345 nm), complex 2 at 428 nm (λex = 360 nm), complex 3 at 508 nm (λex = 304 nm) and complex 4 at 500 nm (λex = 324 nm).Four MII quinolinato complexes, [Zn2(quin)2(H2O)3]n (1), [Zn(quin)(H2O)2]n (2), [Zn(quin)(H2O)]n (3) and [Cd(quin)]n (4) (H2quin = 2,3-pyridinedicarboxylic acid or quinolinic acid), have been hydrothermally synthesized and structurally characterized.
Co-reporter:Jian Zhang, Yao Kang, Rui-Bo Zhang, Zhao-Ji Li, Jian-Kai Cheng and Yuan-Gen Yao
CrystEngComm 2005 vol. 7(Issue 28) pp:177-178
Publication Date(Web):02 Mar 2005
DOI:10.1039/B500273G
A new twisting chiral dense 75.9 net, containing only planar four-coordinate nodes and incorporating single helical sub-structures with the same accessibility, was represented.
Co-reporter:Jian Zhang, Zhao-Ji Li, Jian-Kai Cheng, Yao Kang, Ye-Yan Qin and Yuan-Gen Yao
New Journal of Chemistry 2005 vol. 29(Issue 3) pp:421-423
Publication Date(Web):08 Feb 2005
DOI:10.1039/B415953E
A hydrothermally synthesized mixed-ligand molecular solid has been formulated. The X-ray diffraction analysis of a single crystal revealed a novel 3D architecture generated by unusual 2D bilayer motifs linked up by pillars. Three types of channels in one direction are established inside the structure.
Co-reporter:Xin-Yi Cao, Jian Zhang, Jian-Kai Cheng, Yao Kang and Yuan-Gen Yao
CrystEngComm 2004 vol. 6(Issue 55) pp:315-317
Publication Date(Web):27 Sep 2004
DOI:10.1039/B412700E
A novel zinc coordination supramolecular complex, {[Zn3(OABDC)2(phen)3]·2H2O}n, with an open-ended nanotube architecture based on a nano-sized tetranuclear Zn4(OABDC)4 metallacycle repeating unit, is strategically designed and synthesized using a unique scorpion-shaped carboxylate ligand (5-oxyacetate isophthalic acid = H3OABDC) and phenanthroline.
Co-reporter:Rong Guo, Yeyan Qin, Luyang Qiao, Jianshan Chen, Xiaoman Wu, Yuangen Yao
Catalysis Communications (5 January 2017) Volume 88() pp:94-98
Publication Date(Web):5 January 2017
DOI:10.1016/j.catcom.2016.10.007
•The Pd-Cu/NaY catalysts with better performance were prepared for carbonylation of MN to DMC.•Appropriate amount of Cu species efficiently restricted the size of Pd species.•The oxidation state of Pd2 + could be held by through the reduction-oxidation cycle drove by Cu2 +.•The strength of Pd-CO towards the reaction cycle was tuned by the synergistic effect of Cu.Doping copper in Pd/NaY catalyst has been developed for vapor-phase carbonylation of methyl nitrite (MN) to dimethyl carbonate (DMC). Different characterization methods were employed to investigate the role of Cu in the catalyst. The introduction of Cu2 + could effectively promote the dispersion of Pd species by shrinking the size of Pd species NPs, while the oxidation state of Pd could be maintained simultaneously for better selectivity. Furthermore, the strength of Pd-CO can be tuned by the amount of Cu, which is the most crucial problem towards the reaction cycle.Download high-res image (167KB)Download full-size image
Co-reporter:Xin Zhang, Yuan-Yuan Huang, Qi-Pu Lin, Jian Zhang and Yuan-Gen Yao
Dalton Transactions 2013 - vol. 42(Issue 6) pp:NaN2301-2301
Publication Date(Web):2012/10/12
DOI:10.1039/C2DT31536J
Alkaline-earth metal ions were used to tune four new heterometallic frameworks, {[Cd2.07Mg0.93(BTC)2(H2O)4]·2H2O}n (1), {[Cd2Ca(BTC)2(H2O)4]·2H2O}n (2), {[Cd2Sr(BTC)2(H2O)5]·H2O}n (3) and [Cd6Ba3(BTC)3(H2O)10]n (4) (H3BTC = 1,3,5-benzenetricarboxylic acid), synthesized from H3BTC and the corresponding metal salts. Single-crystal X-ray analysis shows that compound 1 is a three-dimensional (3D) framework based on heterometallic Cd–O–Cd–O–Mg inorganic chain subunits, compounds 2 and 3 are basically isostructural and feature a 3D framework based on Ca(II) or Sr(II) polyhedrons decorated with Cd–O–Cd inorganic chains. Compound 4 is a 3D framework templated by disordered inorganic hydrate Ba(II) ions, and also features inorganic Cd–O–Cd chains, which are connected together through corner sharing with the {Cd1O6} polyhedrons by {Ba1O6} polyhedrons, giving rise to a rare heterometallic 3D inorganic skeleton. Moreover, the solid-state fluorescence of compounds 1–4 and NLO properties of compounds 2–4 have also been investigated at room temperature.
Co-reporter:Jin-Xia Yang, Ji-Quan Zhai, Xin Zhang, Ye-Yan Qin and Yuan-Gen Yao
Dalton Transactions 2016 - vol. 45(Issue 2) pp:NaN723-723
Publication Date(Web):2015/11/04
DOI:10.1039/C5DT03731J
Taking advantage of the conformational flexibility of the bpp ligand and aliphatic dicarboxylic acids, six interesting entangled coordination polymers, {[Cd(fum)(bpp)(H2O)]·(H2O)}n (1), {[Cd(fum)(bpp)2]·(H2O)5}n (2), {[Cd2(suc)1.5(bpp)2(NO3)(H2O)2]·6H2O}n (3), {[Cd(suc)(bpp)2]·(H2O)1.5}n (4), {[Cd2(glu)2(bpp)3]·10H2O}n (5), and {Cd(adp)(bpp)(H2O)}n (6) have been prepared and structurally characterized (bpp = 1,3-bi(4-pyridyl)propane, fum = fumaric, suc = succinate, glu = glutaric, adp = adipic). Compounds 1 and 2 are comprised of undulated 2D 44-sql networks. In the structure of compound 1, two identical undulated layers are parallelly interpenetrated with each other to give a 2D → 2D interpenetrating framework. For 2, the dangling arms projected from 2D layers are intercalated into the neighboring sheets, producing a 2D → 3D polythreading framework. Compound 3 shows a rare example of a 2D self-penetrating framework with a (3,4)-connected (42·63·8)(42·6) topology. Compound 4 presents an unusual 2D self-threading network with a novel 4-connected {42·63·8} topology. Compound 5 displays a 3D self-penetrating system based on a 2D → 3D parallel polycatenation array. Compound 6 exhibits an unprecedented 3D self-penetrating structure having both 1D + 1D → 1D polycatenation and 3D + 3D → 3D interpenetration characteristics. A comparison of these six compounds demonstrates that both the different spacer lengths of the aliphatic dicarboxylates and reactant ratios appear to play a significant role in the assembly of entangled frameworks. In addition, thermal stabilities and photoluminescence properties of 1–6 have been examined in the solid state at room temperature.
Co-reporter:Ye-Yan Qin, Jian Zhang, Zhao-Ji Li, Lei Zhang, Xin-Yi Cao and Yuan-Gen Yao
Chemical Communications 2008(Issue 22) pp:
Publication Date(Web):
DOI:10.1039/B800017D
Co-reporter:Rui-Bo Zhang, Jian Zhang, Zhao-Ji Li, Ye-Yan Qin, Jian-Kai Cheng and Yuan-Gen Yao
Chemical Communications 2008(Issue 35) pp:
Publication Date(Web):
DOI:10.1039/B807320A
Co-reporter:Qiaohong Li, Zhangfeng Zhou, Ruiping Chen, Baozhen Sun, Luyang Qiao, Yuangen Yao and Kechen Wu
Physical Chemistry Chemical Physics 2015 - vol. 17(Issue 14) pp:NaN9134-9134
Publication Date(Web):2015/02/23
DOI:10.1039/C4CP05738D
Oxidative coupling of toxic pollutant CO to form the platform raw chemical material dimethyl oxalate (DMO) has been industrialized however the catalytic mechanism has been unknown so far. The reaction mechanism of CO oxidative coupling to form DMO on a Pd(111) surface has been investigated using density functional theory (DFT) and in situ diffuse reflectance infrared (DRIR) spectroscopy. DFT calculations and in situ DRIRS measurements indicate that two co-adsorbed intermediates COOMe and OCCO, initiate the reaction. C–C coupling occurs earlier due to a low coupling barrier and small steric hindrance. The results also suggest that Pd(111) is selective towards DMO over DMC, and that CO pre-adsorption and CO in excess effectively enhance the yield of DMO. The microscopic elucidation of this important reaction suggests improvements in coal-to-EG (CTEG) production which can be applied in practice to effectively enhance the yield and reduce the cost. The results may help with further fine-tuning and designing of high-efficient noble metal catalysts.
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