Syntheses And Assembly Of The Germanium-Sulfur Clusters

In recent years, Germanium chalcogenide materials have been a hot research topic,due to its application in the field of catalysis, ion exchange, and its potential applicationin semiconductor, nonlinear optics.Germanium chalcogenide compound’s anion is usually constructured to varioustypes of cluster by sharing the corners and the edges of the simple tetrahedral buildingblocks MS₄, which major reported frameworks have two types: Ge2S64-dimer andGe₄S₁₀^4-T₂clusters. The counterions of these chalcogenido germanate are usually thequaternary ammonium cation and protonated organic amines. However, it is lessreported that the structures are hybridized by transition-metal complexs coordinatedwith the conjugated structure organic ligands.1,10-phenanthroline （phen） is a very goodbidentate organic ligand, whose coordination compounds show peculiar photochemicaland electrochemical properities, and widely applied in the field of chemistry andbiology. MV²⁺is a good electron transfer, which are widely used in the field ofchemistry and materials science. In this thesis, seven novel chalcogenidogermaniumclusters assembling the M-phen or MV²⁺complexes were synthesized, andcharacterized by single-structure analysis, whose properties were studied. The majorcontents are as follows:Under room temperature, M-phen is directly incorporated into the structure ofchalcogenidogermanate, and two compounds [Ni（phen）₃]2Ge₄S₁₀·4MeOH·12H2O （1）,[Ni（phen）₃]₂Ge₄S₁₀·24H₂O （2） were obtained. Two related complexes [Fe（phen）₃]·2H₃O[Ge₄S₁₀]·3C₂H₅OH （3） and [Ni（phen）₃]·2H₃O[Ge₄S₁₀]·2C₂H₅OH （4） weresynthesized by a solvothermal method. Compounds1and2show solid-statesolvatochromism and rapid reversible solvent-induced color changes, when crystalimmersed in alcohol and water alternately, reversible color conversion between yellowand pink is found with fast speed. However, such solvatochromism has not been foundfor compounds3and4is not found, which structure are similar to1and2. The solid-state solvatochromism should be applied to preparing environmentally responsivematerials.In room temperature, three compounds [MV]2Ge4S10·MeOH （5）,[MV]₂Ge₄S₁₀·6H₂O （6and6’） are synthesized by diffusion method, and theirconstitutions are similar. Compounds6and6’ are iso-structural, but in different ionpacking. The charge-transfer between chalcogenidogermanium anions and MV2+cations of them have been demonstrated.