Solvothermal Syntheses And Coordination Modifying Of Gallium And Indium Chalcogenides

Gallium and indium chalcogenides and their derivatives as a new type of multifunctional materials have been applied in many fields, because of their unique structures and properties. Flux technique at intermediate or higher temperatures, cathodic dissolution and hydroythermal or solvothermal reactions are most important routes to obtain this kind compounds, which have been used as catalyzers, film cells of solar energy, photoelectronic conductors, nonlinear optical materials, adsorption, ion exchange and so on. In 1989, Bedard et al firstly used hydrothermal method to obtain germanium and stannum chalcogenides using tetra-alkylammonium R4N+(R = Me, Et, Pr, ect) as structure-directing agents or templates. Since their discovery, Hydro- or solvothermal synthesis of chalcogenides has become accordingly a very effective method for gallium and indium chalcogenides. These compounds usually are based on MQ4 (M = In, Ga; Q = S, Se, Te) tetrahedral primary building units. These tetrahedra exhibit a characteristic tendency of corner- or edge- sharing and a variety of structures of the chalcogenidometalate are formed, whose counterions are usually the protonated organic amines, tetra-alkylammonium and metal complexes. Although the work of many chalcogenidometalates has been reported, this field need be further studied to make them deep, systemic and flourishing. Therefore the work of this thesis focuses on the synthesis of novel gallium and indium chalcogenides under solvothermal condition. Their reaction conditions, thermal stabilities and optic properties are discussed. The major contents are as follows:1.In In/Q(Te, Se) solvothermal reaction systems, five indium chalcogenides [{In(dien)}2(InTe4)]·Cl(1),[{In(dien)}2(InTe4)]·Br(2), [InTe(en)2]2·2I(3),[In(en)2Se] 2·2I(4) and [In(teta)Se]2·2I(5) were obtained. In compound 1,the cationic chain structure can be viewed as a string of fused eight-membered In4Te4 rings, in which the cation [{In(dien)}2(InTe4)]+ propagates along the crystallographic c axis. The chains are assembled to a 2-D extended layer structure via hydrogen-bond interactions with Cl- anions. The structure of compound 2 is similar to compound 1. Because of I- ions introduced, compounds 3~5 have a dimeric cation with a similar In2Te2 rhomboidal core, which are different from compounds 1 and 2. The results indicated a halogen-ion-effect for the structure of In?Q(Te, Se)?amine compounds. The cationic chalcogenide structures are first discovered based on our knowledge. The indium(III) ion is coordinated by chelating amine and chalcogenidometalate moiety and then forms a structures with positive charge. This work not only obtains new organic hybrid chalcogenidometalates, but also widens the study on the field.2.Two chalcogenides with lanthanide metal complexes [Dy2(en)6(μ2-OH)2]Ga4S8(6) and {[SmCl(en)4][In2Te4]}n(7) were obtained. At the similar reaction conditions except the temperature two binary telluridoindate [In(en)3][In5Te9·2en] (8) [InTe2]2·enH2(9) were obtained. In compound 6, dimeric metal complex [Dy2(en)6(μ2-OH)2]4+ is composed of OH- ions bridging and [GaS2]- anion are affected presenting a sinusoidal 1-D structure. Metal complex cation template effects been shown in compound 7 with N-H···Cl hydrogen bonding. Compound 8 has a rare 2D layer structure composed of T1 and T2 cluster and compound 9 is a simple straight chain.3.Using organic amines as structure-direct agent, three binary indium selenides [(1, 2-dapH2)4][In10Se19](10), [EOAH]7[In11Se20](11) and (AEAEH2)3.5[In17Se29](12) were obtained. Compound 10 shows a three-dimensional open framework built of T3 supertetrahedral clusters. The pore volume occupies 8144.6 ?3 in a unit cell and the percentage is 55.5%. Compound 11 and 12 are more complicated three-dimensional open framework structures, in which the pore volumes of a unit cell occupy 7355.9 ?3 (48.9%) and 4878.7 ?3 (48.8%), respectively. Inorganic acids H3BO3 and HI are used to adjust pH values of the reaction systems.4. In N,N-Dimethylformamide (DMF) system, three compounds [Ni(phen)3]4[In10S19] (15),Mn(bpy)[S2CN(CH3)2]2 (14) and Mn(phen)[S2CN(CH3)2]2 (15) were obtained. Compound 14 and 15 are similar and their ligand [S2CN(CH3)2]- was generated in-situ reaction synthesis (DMF-CS2). Compound 13 is a one-dimensional T3 cluster chain with Ni(phen)32+ complex cations. The M(phen)32+ cations were firstly introduced to gallium and indium chalcogenides, and will afford in excellent photoelectronoc property and extend the uses of organic composition .This work focuses on the syntheses and research of gallium and indium chalcogenides. Fifteen new compounds were synthesized and their structures, electronic spectra and stability were characterized. It is important for the further exploring of gallium and indium chalcogenides.