Solvothermal Synthesis Of Indium Chalcogenides Integrated With 2,2'–Bipyridine

Interest in gallium and indium chalcogenido clusters is rapidly increasing because of their intriguing architectures and excellent photoelectronic properties. Supertetrahedral clusters denoted as Tn (n = 2-5) are the main building-block for constructing gallium and indium chalcogenide clusters. These compounds exhibit a variety of structures with a tendency of corner- or edge-sharing. The counterions of these chalcogenidometalates are usually the protonated organic amines and metal amine complexes. But little is known about related chalcogenidometalates integrated with metal complexes of 2,2'-bipyridine (bpy). The bpy is an excellent chelating agent and the presence of 12 electrons delocalized over the aromatic ring confers peculiar spectroscopic, photochemical, and electrochemical properties on bpy-based metal complexes.In this thesis, we introduced bpy into indium chalcogenides and studied their structures and spectral properties. The major contents we researched were as follows: In introduction, the research progresses in crystal structures and properties of gallium and indium chalcogenides are described; the roles of organic amines, the properties and applications of bpy are reviewed briefly.In chapter 2, under solvothermal condition, organic ligand bpy was introduced into indium chalcogenido clusters and compounds [InSe(bpy)Cl]₄ (1) and [InS(bpy)Cl]₄·H₂O (2) were obtained. Compounds 1 and 2 are cubic structures and belongs to the unusual S4 point group. Spectroscopic study indicates that introducing bpy into chalcogenido clusters significantly decreases the energy gap of the frontier orbitals due to cluster–ligand charge transfer.In chapter 3, three compounds with [Ni(bpy)₃]²⁺ cation: [Ni(bpy)₃]₃[H₄In₁₀S₂₀]·bpy·2EG·6H₂O (3) , [Ni(bpy)₃]2[H₂In₁₀S₁₉]·bpy·2HEA·2H₂O (4) , [Ni(bpy)₃]9[H4In₄₀S₇₄]·Hbpy·5HEA·8H₂O (5), and three compounds with [Ru(bpy)₃]²⁺ cation: {[Ru(bpy)₃]₃·2bpy·H4In₁₀S20}·11H₂O (6), {[Ru(bpy)₃]₂·4Hbpy·In₁₀S₁₉}n (7), and {[Ru(bpy)₃]2·2Hbpy·H₂In₁₀S₁₉·10H₂O }n (8) were obtained by solvothermal reactions. Compound 5 shows unique 2D structure and compounds 6⁸ are first reported Tn compounds with [Ru(bpy)₃]²⁺ cation. Charge-transfer exists between M-bpy cations and the cluster anions in this organic-inorganic hybrid material, which makes these compounds possess unique spectral properties.