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)]center dot 0.5DMSO}(n) (2) were achieved by interdiffusion reaction of (NH4)(2)WS4 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. (C) 2016 Elsevier Ltd. All rights reserved.