………………………………………………………………………………………… ABSTRACT: The systematic study on the reaction variables affecting single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers (CPs) is firstly demonstrated. Five anionic single cyanide-bridged Mo(W)/S/Cu cluster-based CPs {[Pr 4 N][WS 4 Cu 3 (CN) 2 ]} n (1), {[Pr 4 N][WS 4 Cu 4 (CN) 3 ]} n (2), {[Pr 4 N][WOS 3 Cu 3 (CN) 2 ]} n (3), {[Bu 4 N][WOS 3 Cu 3 (CN) 2 ]} n (4) and {[Bu 4 N][MoOS 3 Cu 3 (CN) 2 ]} n (5) were prepared by varying the molar ratios of the starting materials, and the specific cations, cluster building blocks and central metal atoms in the cluster building blocks. 1 possesses an anionic 3D diamondoid framework constructed from 4-connected T-shaped clusters [WS 4 Cu 3 ] + and single CNbridges. 2 is fabricated from 6-connected planar 'open' clusters [WS 4 Cu 4 ] 2+ and single CN -bridges, forming an anionic 3D architecture with an "ACS" topology. 3 and 4 exhibit novel anionic 2-D double-layer networks, both constructed from nest-shaped clusters [WOS 3 Cu 3 ] + linked by single CN -bridges, but containing the different cations [Pr 4 N] + and [Bu 4 N] + , respectively. 5 is constructed from nest-shaped clusters [MoOS 3 Cu 3 ] + and single CN -bridges, with an anionic 3D diamondoid framework. The anionic frameworks of 1-5, all sustained by single CN -bridges, are non-interpenetrating and exhibit huge potential void volumes. Employing differing 2 molar ratios of the reactants and varying the cluster building blocks resulted in differing single cyanide-bridged Mo(W)/S/Cu cluster-based CPs, while replacing the cation ([Pr 4 N] + vs. [Bu 4 N] + ) was found to have negligible impact on the nature of the architecture. Unexpectedly, replacement of the central metal atom (W vs. Mo) in the cluster building blocks had a pronounced effect on the framework. Furthermore, the photocatalytic activities of heterothiometallic cluster-based CPs were firstly explored by monitoring the photodegradation of methylene blue (MB) under visible lightirradiation, which reveals that 2 exhibits effective photocatalytic properties.
Properties. -Single cyanide-bridged Mo(W)/S/Cu cluster-based compounds are synthesized by varying the starting materials and their molar ratios, and characterized by single crystal XRD. Compounds (IVa) and (IVc) crystallize in the orthorhombic space group P2 12121 with Z = 4. Compound (IVb) crystallizes in the orthorhombic space group Pbca with Z = 8, (V) in the orthorhombic space group Pnma with Z = 4, and (VII) in the monoclinic space group P2 1/c with Z = 8. Compound (IVa) has an anionic three-dimensional diamondoid framework constructed from 4-connected T-shaped [WS 4Cu3] + clusters and single CNbridges. (V) contains 6-connected planar [WS 4Cu4] 2+ clusters and single CNbridges, forming an anionic three-dimensional architecture. (IVb) and (VII) exhibit novel anionic two-dimensional double-layer networks constructed from [WOS 3Cu3] + clusters linked by single CNbridges. (IVc) contains [MoOS 3Cu3] + clusters and single CNbridges, forming an anionic three--dimensional diamondoid framework. Compound (V) shows effective photocatalytic activity and recyclability in the degradation of methylene blue under visible light irradiation. -(ZHANG*, J.; WANG, C.; WANG, Y.; CHEN, W.; CIFUENTES, M. P.; HUMPHREY, M. G.; ZHANG, C.; J. Solid State Chem. 231 (2015) 230-238, http://dx.
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