Solvothermal Synthesis, Characterzation And Crystal Structure Of Multinary Thio-tellurite Compounds

Multinary chalcogenides have attracted increasing attention because of their potential applications in the fields of optoelectronic materials, molecule-discriminating catalysis, ion exchangers, nonlinear optical (NLO), and semiconductors. Solvohtemral synhtesis techique is an effictive method to creat metastable materials. To develop the solvothermal synthesis studys of multinary chalcogenides, it can enrich the structural chemistry of chalcogenides and have actual significance for discovering the novel inorganic function material. Herein a series of multinary thio-tellurates were synthesized by solvothermal reaction, and their structures and properties were characterized by elemental analysis、XRD、IR、DSC、TGA and UV-Vis.(1) In the A/Te/S(A=organic amine) system, a novel thiotellurite compound (enH2)TeS3(1) was obtained under solvothermal conditions in the presence of ethylenediamine as structure-directing agents and1,2-ethanedithiol/pyridine (1:2in volume ratio) as solvent at110℃. Compound1crystallizes in the monoclinic system, space group P21.The trigonal-pyramidal [TeS3]2-anions were fixed by the cations [H2en]2+. In compound1, the bio-protonated amine of [H2en]2+and [TeS3]2" are connected by N-H…S hydrogen bonds. Compound1was breaking at190℃, and UV-vis reflectance spectroscopy reveals compound1was a semiconductor.(2) In the A/M/Te/S (A=organic amine, M=transition metal) system, we have successfully synthesized a new quaternary thiotellurite [Ni(en)3]TeS3(2), transition metal complex with mixed ethylenediamine in solvothermal condition. Compound2crystallizes in the monoclinic system, space group P21/c. The crystal structure of compound2was consist of discrete trigonal-pyramidal [TeS3]2" anion and isolated [Ni(en)3]2+cation. Compound2was breaking at208℃,UV-vis reflectance spectroscopy reveals compound2was a semiconductor material. And the photocatalytic properties of compound2has been discussed.Based on the this synthetic route,we have studied in A/M/Te/S (A=organic amine, M=transition metal) system, with other transition metal elements. And obtained two multiple thio-tellurite compounds en-Mn-Te-S(3) and en-Co-Te-S (4).(3)We carried out the research of A/M/Te/S system (A=alkali metal or alkaline earth metal, M=transition metal), two new quaternary thiotellurites Cs-Ag-Te-S (5) and Cs-Cu-Te-S (6) were synthesized on the basis of this synthetic route.