Syntheses, Crystal Sturctures And Photocatalytic Properties Of Heterothiometallic W/S/Cu Clusters

Heterothiometallic clusters have attracted great attention not only for their aesthetic architectures, but also for potential applications in material science. Heterothiometallic W/S/Cu clusters have been extensively explored in the recent years owing to their fascinating structures as well as promising applications in the fields of adsorption, solvatochromism and nonlinear optical(NLO) materials, etc. In this article, we report the syntheses and single-crystal X-ray diffraction studies of eight unusual W/S/Cu clusters, namely(1) {[WS4Cu4Cl2(phen)2]2·MeCN}(2) {[WS4Cu4Br2(phen)2]2·Me CN}2(3) {[Cu Cl(phen)2]2[WOS3Cu3Cl2(phen)]2}(4) {[Cu Br(phen)2]2[WOS3Cu3Br2(phen)]2}(5) {[WS4Cu4(SCN)2(2,2’-bipy)2]2}n(6) {[WS4Cu4(4,4’-bipy)4][WS4Cu4(SCN)4(4,4’-bipy)2]}n(7) {[Ca(DMAC)6]2[W4S16Cu4]}(8) {[WS4Cu3]2(Py)9[N(CN)2]2}All the complexes were characterized by elemental analyses, IR, UV-vis, powder and single crystal X-ray diffractions.1. 1 and 2 exhibit rare dimeric architectures, constructed by two parallel pentanuclear planar ‘open’ [WS4Cu4]2+ clusters linked together via a pair of μ2-Cl/μ2-Br bridges. While 3 and 4 consist of the five-coordinated cations [Cu Cl(phen)2]+/[Cu Br(phen)2]+ and the dimeric anionic clusters {[WOS3Cu3Cl2(phen)]2}2-/{[WOS3Cu3Br2(phen)]2}2-, which are fabricated by a pair of tetranuclear nest-shaped clusters connected by two μ2-Cl/μ2-Br bridges. Moreover, the photocatalytic activities of heterothiometallic clusters were firstly explored by monitoring the photodegradation of methylene blue(MB), which reveals that 1-4 all exhibit effective photocatalytic properties under visible light irradiation. 2. 5 shows a novel 1-D twin-line architecture, constructed by 2,2’-bipy chelated ligands,-SCN bridges and pentanuclear planar ‘open’ [WS4Cu4]2+ clusters. While, complex 6 is an unusual 3D diamondoid cluster coordination polymers, which contains four independent interpenetrating cationic and anionic diamond nets. The cationic nets are constructed by [WS4Cu4]2+ clusters linked by double 4,4’-bipy ligands, while anionic nets are constructed by [WS4Cu4(SCN)4]2- clusters linked by single 4,4’-bipy ligands. 3. Clusters 7 and 8 both exhibit distinct oligomeric W/S/Cu atchitectures. 7 contains two [Ca(DMAC)6]2+ cations and a tetrameric anionic cluster [W4S16Cu4]4-, which shows the unusual octanuclear planar ‘open’ square-like skeleton. As a template, [Ca(DMAC)6]2+ plays a crutial role in constructing anionic cluster [W4S16Cu4]4-. The novel dimeric architecture of 8 consists of two T-shaped [WS4Cu3]+ clusters linked through μ2-N(CN)2 bridge.