Four distinct anionic heterothiometallic W/S/Ag polymeric clusters directed by solvent-coordinated metal cations

The solvent-coordinated metal cations as templates affecting the architectures of anionic heterothiometallic Mo(W)/S/Ag polymeric clusters was investigated. Four W/S/Ag polymeric clusters {[Tb(DMSO)8][W3S12Ag3]}n (1, DMSO = dimethyl sulfoxide), {[Tb(DMF)8][W3S12Ag3]}n (2, DMF = N,N′-dimethylformamide), {[Tb(NMP)8][W4S16Ag5]}n (3, NMP = N-methyl-2-pyrrolidone) and {[Mg(NMP)6][W2S8Ag2]·2NMP}n (4) with distinct 1-D anionic structures were obtained by the reactions of (NH4)2WS4, AgI and M(NO3)x (M = Tb, x = 3; M = Mg, x = 2) in corresponding solvents (DMSO, DMF or NMP). 1–4 were determined by elemental analysis, IR, UV–Vis, thermogravimetric analysis, X-ray powder and single crystal diffractions. Directed by different solvent-coordinated trivalent terbium metal cations, 1 shows a 1-D anionic helical chain architecture; 2 exhibits a 1-D anionic zigzag chain with hexanuclear [W3S12Ag3]3− repeated units; 3 possesses another kind of 1-D anionic zigzag chain with the unique nonanuclear planar square-like [W4S16Ag5]3− repeated units. While induced by NMP-coordinated bivalent magnesium metal cation, 4 exhibits a 1-D anionic linear chain structure.

Graphical abstractThe types of coordinated solvents and the valences of central metals in the cationic templates were shown to have the pronounced effects on the skeletons of 1-D anionic W/S/Ag polymeric clusters.Figure optionsDownload full-size imageDownload as PowerPoint slide