| Coordination polymers(CPs) as a kind of crystal materials with excellent properties have received extensive attention in the field of modern chemistry and materials science. W(Mo)/S/Cu(Ag) cluster-based CPs could be constructed by various W(Mo)/S/Cu(Ag) cluster building units, organic and inorganic bridged ligands through different synthetic methods. Therefore, W(Mo)/S/Cu(Ag) cluster-based CPs have attracted considerable attention for their fascinating architectures, as well as widespread applications in nonlinear optics, photocatalysis, gas sorption and semiconductor materials, etc. In this article, we report the synthesis and crystal structures of eleven unusual W(Mo)/S/Cu(Ag) cluster-based CPs, namely(1) [W2S8Cu8(CN)4(3-abpt)·CH3CN·H2O]n(2) [Mo2S8Cu8(CN)4(3-abpt)·H2O]n(3) [WS4Cu3(CN)(4,4′-bipy)2]n(4) [WS4Cu4(SCN)4Eu2(INA)4(HMPA)8·2HMPA]n(5) [WS4Cu4(SCN)4Tb2(INA)4(HMPA)8]n(6) [WS4Cu4(CN)3Eu(NA)2(DMSO)4·DMSO]n(7) [WS4Cu4(CN)3Sm(3-paa)2(DMSO)4·DMSO]n(8) [W2S8Cu8(CN)5Tb2(INA)7(DMSO)3(H2O)·2DMSO·6CH3CN·9H2O]n(9) [(WS4Cu4)2(SCN)4Mg3(INA)8(H2O)2]n(10) {[Tb(NMP)8][W4S16Ag5]}n(11) {[Tb(DMSO)8][W3S12Ag3]}n All compounds were characterized by FT-IR, UV-vis, elemental analysis, thermogravimetric analysis, single and powder crystal X-ray diffractions, and the luminescence sensing properties of W(Mo)/S/Cu clusters-based CPs were firstly explored.1. The influence on the structures of W(Mo)/S/Cu clusters-based CPs by the bispyridine bridged ligands had been studied.Through solvothermal synthesis method, the first dimeric decanuclear cluster [M2S8Cu8]4+-based(M = W or Mo) isostructural W(Mo)/S/Cu clusters-based CPs 1 and 2 were achieved by the multidentate ligand 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole(3-abpt), the structural study reveals that 1 and 2 show the unprecedented 3-D frameworks with binodal(3, 11)-connected topology. While W/S/Cu clusters-based CP 3 shows the first T-shaped cluster [WS4Cu3]+-based 2-D(4, 4) network, which is fabricated by the bidentate ligand 4,4′-bipy. Moreover, 1 and 2 exhibit sensitive luminescence sensing properties for nitro aromatic explosives.2. The cluster-metal CPs with W/S/Cu cluster building units and rare earth metal building units had been firstly designed and synthesized.The isostructural cluster-metal CPs 4 and 5 with W/S/Cu cluster building units and rare earth metal building units had been firstly constructed by bifunctional ligand isonicotinic acid with pyridyl and carboxyl. The structural study exhibits an unusual 3-D fourfold interpenetrated diamondoid architecture. 4 and 5 have luminescence sensing properties for nitro aromatic explosives, and exhibit highly sensitive response to picric acid.3. The heterobicluster CPs with W/S/Cu cluster building units and rare earth/alkaline earth metal cluster building units had been firstly designed and synthesized.Four unique heterobicluster CPs 6-9 were firstly constructed by angular rigid bifunctional ligand nicotinic acid, angular flexible bifunctional ligand 3-pyridineacetic acid, and linear rigid bifunctional ligand isonicotinic acid, respectively. 6-9 are all constructed by pentanuclear planar open-shaped [WS4Cu4]2+ clusters but distinct rare earth/alkaline earth metal clusters. 6 displays a 3-D neutral diamondoid framework, 7 and 8 reveal different 3-D binodal(4, 5)-connected frameworks, and 9 exhibits the first 2-D binodal(5, 6)-connected network.4. The influence on the structures of W/S/Ag cluster-based CPs by solvent-coordinated metal cations had been studied.Directed by different solvent-coordinated terbium metal cations [Tb(NMP)8]3+ and [Tb(DMSO)8]3+, 10 possesses a 1-D anionic zigzag chain with the unique nonanuclear planar square-like [W4S16Ag5]3- repeated clusters and 11 reveals a 1-D anionic helical chain architecture. |
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