Construction of two unique W/S/Cu cluster-based coordination polymers affected by pseudohalogen ligands

The pseudohalogen ligands affecting the architectures of heterothiometallic Mo(W)/S/Cu(Ag) cluster-based coordination polymers (CPs) was firstly explored. In the presence of CuCN or CuSCN with distinct pseudohalogen ligands, two unique W/S/Cu cluster-based CPs [WS4Cu3(CN)(4,4′-bipy)2]n (1, 4,4′-bipy = 4,4′-bipyridine) and {[WS4Cu4(4,4′-bipy)4][WS4Cu4(SCN)4(4,4′-bipy)2]·0.5DMSO}n (2) were achieved by interdiffusion reaction of (NH4)2WS4 and 4,4′-bipy. 1 and 2 were characterized by X-ray single and powder crystal diffractions, elemental analysis, IR, UV–Vis, thermogravimetric analysis. 1 exhibits a neutral 2-D (4,4) network, fabricated by 4-connected T-shaped [WS4Cu3]+ clusters, single CN− bridges and double 4,4′-bipy bridges. While, 2 possesses an unusual 3-D fourfold non-equivalent interpenetrated architecture, consisting of two cationic and two anionic planar ‘open’ [WS4Cu4]2+ cluster-based frameworks; the cationic and anionic architectures are constructed by double 4,4′-bipy bridges and single 4,4′-bipy bridges, respectively, and all show the diamondoid topologies.

The pseudohalogen ligands affecting the architectures of Mo(W)/S/Cu(Ag) cluster-based coordination polymers (CPs) was firstly explored, which results in a 2-D T-shaped [WS4Cu3]+ cluster-based (4,4) network and a 3-D planar ‘open’ [WS4Cu4]2+ cluster-based CP with very scarce non-equivalent cationic and anionic interpenetrated framework.Figure optionsDownload as PowerPoint slide