Solvothermal Synthesis, Crystal Structures Of Gallium And Indium Functional Chalcogenides

Great interest is devoted to obtaining gallium and indium chalcogenides by solvothermal reactions due to their excellent photoelectronic properties in recent years. These compounds are usually based on MQ₄ （M = In, Ga; Q = S, Se, Te） tetrahedral building blocks, which exhibit a characteristic tendency of corner- or edge- sharing. A variety of structures of the chalcogenidometalate are formed, whose counterions are usually the protonated organic amines, tetra-alkylammonium and metal amine complexes. But little is known about related chalcogenidometalates integrated with metal complexes of 1,10-phenanthroline （phen）. The phen is an excellent chelating agent and the presence of 14 electrons delocalized over the aromatic ring confers peculiar spectroscopic, photochemical, and electrochemical properties on phen-based metal complexes.In this thesis, we introduced phen into gallium and 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 phen are reviewed briefly.In chapter 2, under solvothermal condition, organic ligand phen was introduced into gallium and indium chalcogenido clusters and obtained compounds [InSe（phen）Cl]₄ （1）、[InS（phen）Cl]₄·1.5C₂H₆O₂·0.5 H₂O （2） as well as four related complexes[In（phen）₂Cl₂]I₃ （3）、[Ni（phen）₃]·[In（phen）Cl₄]Cl·2（CH₃CN）·H₂O（4）、[Ga（phen）₂Cl₂]I₃·H₂O （5）、[Ga（phen）₃]（ClO₄）₃·H₂O （6）. The symmetry of the clusters of compounds 1 and 2 belongs to the unusual S4 point group. Compound 1 forms a chiral structure. A spectroscopic study indicates that introducing phen into chalcogenido clusters significantly decreases the energy gap of the frontier orbitals due to cluster–ligand charge transfer.In chapter 3, introducing transition-metal complexes of phen to InS cluster by solvothermal reactions obtained two metal clusters{[Ni（phen）₃]₃·H₄In₁₀S₂₀}·2DMA·7H₂O （7） and {[Ni（phen）₃]₃·H₄In₁₀S₂₀}·14.5H₂O （8） as well as three related complexes [Ni（phen）₂Se₄] （9） and [Mn（phen）₂Se₄] （10）、[Mn（phen）₂S₆] （11）. We discovered that transition metal complex cation could stabilize the isolated T3 In₁₀S₂₀ cluster. Intense charge-transfer exists between [Ni（phen）₃]²⁺ cations and the cluster anions in this organic-inorganic crystalline material, which makes these compounds possess unique spectral properties.