Syntheses Of Coordination Modified Indium Chalcogenide Compounds

Organic-inorganic hybrid materials are one of the most active research fields inmaterials science in recent years. Organic hybrid chalcogenide materials have beenattracted considerable interests not only due to their novel structures but also due totheir unique physical and chemical properties, such as catalysis, adsorption, ionexchange, photoluminescence, nonlinear optics and semiconductor. The syntheses ofthese materials are typically carried out under hydro（solvo）thermal conditions usingstructure directing agent （or template） of the organic amines or quaternary ammoniumsalts. Tetrahedral ortho-anions MQ4（M=Ga, In, Sn, Sb; Q=S, Se, Te） or pyramidanions MQ3（M=Sb; Q=S, Se） as primary building units exhibit a characteristictendency to condense through corner-or edge-sharing to afford a variety of structures ofthe chalcogenidometalate anions. In the research of main group chalcogenides, designand synthesis of open-framework structure and nano clusters is the frontier and trend incurrent research, in which the metal sulfides modified with transition metal coordinationmoieties have been the focus of research. The nanometer supertetrahedral clusters andwheel-like clusters with the novel structure types and sizes are becoming a new researchdirection to the development of nanostructured materials. In the synthetic methods formain group chalcogenides, selecting new amine system and using ionic liquid mediumare very important to prepare new organic-inorganic hybrid materials. The research goalof this work is the synthesis of indium chalcogenide clusters or compounds modified bycoordination complexes. Supertetrahedral cluster compounds with novel linkages andwheel-shaped indium chalcogenide clusters were synthesized by selecting1,2-diaminocyclohexane （dach） as the reaction solvent and chelating agent. The synthesisconditions, influence factors, such as using or without using GeO₂and ionic liquids,compound structure, thermal stability and optical properties were discussed. The maincontents of this thesis are as follows:1.The solvothermal synthetic methods of chalcogenide compounds, and the application of organic amine compounds and ionic liquids in the syntheses are brieflyreviewed. The structure characteristics of gallium, indium chalcogenides aresummarized. The research progress in synthesis of wheel-like chalcogenide clusters isalso reviewed2. Supertetrahedral cluster compounds with T4-complex-T4structure weresynthesized by metal complex assembly in In/S/dach/M（M=Fe, Co） systems.Compound1{[In₁₆Fe₄S₃₄H₂]₂[Fe（dach）₂]₃}₄[Fe（dach）₃]6Hdach6H₂O is an2Dsupertetrahedral cluster formed from T4clusters connected by [Fe（dach）₂]²⁺, andcompound2{[In₁₇Co₄S₃₈H₃]₂[Co（dach）₂]}·8[Co（dach）₃]10Hdach·2H₂O is a discretemolecular, a [Co（dach）₂]²⁺bridged two T4clusters. The in-situ formed [Fe（dach）₂]²⁺complex cations act as linkages joining the T4clusters is the first example for suchcompounds. Furthermore, integrating transition metal complexes into structure of maingroup metal chalcogenides clearly improves the optical functionality of thesecompounds.3. Novel supertetrahedral cluster compounds were synthesized in In/S/dach/M（M=Ni, Co） systems, using L-cysteine （L-cyst.） as sulfur source, and two materials （GeO₂and ionic liquid） an auxiliary. The anion of [In12S20（dach）2]·H2dach·[Ni（dach）3]·3H2O（3） is a3-D framework assembled by T3clusters and the linkage of the In4（dach）4S6cluster. The anion of [In₁₆Co₄S₃₇]·2Hdach·4[Co（dach）₃]·dach·5H₂O （5） is a2-Dframework assembled by T4clusters connected by unusual （S3）2–polysulfide ion. Thestructures of other two new compounds,[In2S4]·[Ni（dach）₃]（4） and{[In₁₆Co₄S₃₄]₂[Co（dach）₂]₃}·4Hdach·6[Co（dach）₃]·6H₂O （6） are known. The auxiliariesplay an important role in the structural assembly of the Tn clusters, mainly due to theireffects on acidity and polarity of the reaction system and solubility of the reactants orproducts.4. Ligand modified new type InTe clusters were synthesized in In/Te/dach systems.They are wheel-shaped indium telluride nano clusters7[Mn（dach）₃]₂[In₁₈Te₃₀（dach）6]·2Hdach·H2O and8[Ni（dach）₃]₂[In₁₈Te₃₀（dach）₃]·2Hdach. A notablefeature of compound7and8is the nano scale ring size （ca.1.5nm）. It is notable thatcompound7and8are the first large nanoring compound found for main-group metal chalcogenides, in which the bridge is the inorganic divalent tellurium anion. The dachmolecules play important roles in the formation of the wheel-like topology. The weakacidity is the point for the formation of7and8, because at higher acidity, the dachmolecules are protonated and difficult to coordinate to the In atom. At higher acidity, a1-D compound9{[Mn（dach）₃]₂[In₅Te₁₀]·2H₂O}∞was prepared under similarsolvothermal condition.5. Ligand modified InSe wheel-shaped clusters were synthesized in In/Se/dachsystems. The indium selenide10,[Mn（dach_）3]₉[In₃₀Se₇₂（dach）₃]₂[In₁₈Se₃₀（dach）₆]·2H₂O,contains two different size nano wheels and is the first large nanoring compound foundfor InSe clusters, with average outer diameter25.78（2.58nm）. The nanoscaleinorganic cluster shows a double-decker ring structure, and the matrix in the singlecrystal might have applications as optical and photoelectron conversion.