The Solvothermal Syntheses And Characterizations Of Transition Metal-contained Chalcogenidoarsenates

Recently extensive interest has been focused upon the Main Group chalcogenidometalates due to their promising photoconductivity, photoluminescence and nonlinear optical properties. The solvothermal reaction is becoming a versatile route to the chalcogenidometalates. The incorporation of transition metals with chalcogenidometalates will not only give rise to the change of structure, but also endue chalcogenidometalates with new properties. In this work, the major studies are as follows:1. The chalcogenidoarsenates [Fe(en)₃]2As₂S₅(1), [Co(dien)₂]As₂Se₆(2) ,[Ni(dien)₂]As₂Se₆(3) and [Mn(dap)₃]As₂Se₆(4) with the [As₂S₅]^4-and [As₂Se₆]^2-anions were synthesized by solvothermal method in en, dien and dap solvents.Discussing the influence of ethylene polyamines and the starting materials on the chalcogenidoarsenates.2. The transition metal-contained thioarsenates [Fe(phen)₃][As3S6]-dien-7H2O(5) and [Mn₂(phen)4(As₂S₅)]-phen-2H₂O(6) were synthesized using the ligand 1,10-phenanthroline (phen) under hydrothermal conditions. 1,10-Phenanthroline was first used in the preparation of compand 5 which contains an infinite 1D chain of water molecules under hydrothermal conditions. The [As₂S₅]^4– anion acts as a tetradentate brigding ligand in the compand 6 and discuss the influence of the organic ligands on the thioarsenates.3. The transition metal-contained selenidoarsenates [Ni(phen)₃][As₂Se₂(μ-Se₃)(μ-Se₅)](7), [Ni(phen)₃]2As₈Se₁₄(8), [Mn-2(phen)₄(μ-η²,η²-AsSe₄)]₂[As₂Se₆]-H₂O(9), [Zn(phen)(dien)]As₂Se₆·2phen(10) and [Fe(phen)₃]As₂Se₆(11) were synthesized using the ligand 1,10-phenanthroline under solvothermal conditions. Polyselenidoarsenates 7, 9, 10, 11 were synthesized in CH₃OH solvent and selenidoarsenate 8 were synthesized in H2O solvent. The novel polyselenidoarsenate chain [As₂Se₂(μ-Se₃)(μ-Se₅)₂-]∞with μ-Se₃^2-å'ŒÎ¼-Se₅^2- and a new selenidoarsenate aggregate [As₈Se₁₄]^4– with condensation grade of above 0.50 are observed in 7 and 8 respectively.4. The synthesized chalcogenidoarsenates were characterized by elemental analysis, IR and X-ray crystallographic, and their thermal stability were also investigated.