Syntheses And Assembly Of The Germanium-sulfur Heteronuclear Compounds

In recent years, germanium-sulfur materials have been a hot research topic, due to itsapplication in the field of photoelectronic, ion exchange and catalysis. Thiogermanatecompound’s anions are usually constructured to various types of clusters by sharing thecorners and the edges of the simple tetrahedral building blocks GeS4, which major reportedframeworks have two types: dimer (Ge2S64-) and T2clusters (Ge4S104-). The research ofthiogermanate compounds have two scopes: first, anion framework changing from binaryGe-S to complex Ge-M-S in order to achieve novel and changable structure; second, theintegrating of organic functional molecules or transition-metal complexs intogermanium-sulfur clusters as cations for exploring their properties.MV2+and DMBPE2+are good electron acceptor, which are widely used in the field ofchemistry and materials science. Moreover, M-phen and M-dien are also widely used inmany fields of optical materials. In this paper, the organic functional molecules (MV2+orDMBPE2+) are self-assembled with Ge-S aniom clusters to obtain novel functional clusters.The M-dien and M-phen are integrated into multiple Ge-Sb-S and Ge-Sn-S aniom clustersto harvest novel germanium-sulfur heteronuclear clusters. Their syntheses, crystal structuresand properties were discussed. The major contents are as follows:Part1, as a continued work, five compounds [MV]2Ge4S106H2O (1and1’),[MV]2Ge4S10MeOH (2)、[DMBPE]2Ge4S108H2O(3) and [DMBPE]2Ge4S105H2O(3’) aresynthesized in room temperature. Sharp and fast solvent-induced color changes(solvatochromism) and switchable fluorescence emission (solvatofluorochromism) areobserved for the compounds. The changes for compounds3are not obvious as that of1.The photocurrent measurement shows that the compounds are all photoelectric activefeaturing their D-A properties.Part2, three related complexes [M(dien)2]3[Ge5Sb6S21](M=Ni,4;Co,5) and[Ni(phen)3][GeSn2S6](6) are synthesized by a solvothermal method, and they both havenovel structures. The difference is that the compounds4and5consist of2D Ge-Sb-S anion structures and [M(dien)2]2+cations, while compound6consist of1D Ge-Sn-S anionchains and [Ni(phen)3]2+cations. They also show photoelectric activity.