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Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of Chalcogenidoplumbates(II or IV)
Published on: December 29, 2016
Solvothermal synthesis and characterization of polyselenidoarsenate salts of transition metal complex cations
Dingxian Jia1, Jing Zhao, Yingli Pan
1Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Dushu Lake Campus, Soochow University, Suzhou 215123, PR China. jiadingxian@suda.edu.cn
Abstract:
The polyselenidoarsenates [Fe(phen)(3)][As(2)Se(6)] (1), [Zn(phen)(dien)][As(2)Se(6)]·2phen (2), [{Mn(phen)(2)}(2)(μ-η(2),η(2)-AsSe(4))](2)[As(2)Se(6)]·H(2)O (3), and [Ni(phen)(3)][As(2)Se(2)(μ-Se(3))(μ-Se(5))] (4) (dien = diethylenetriamine and phen = 1,10-phenanthroline) were prepared by the reaction of As(2)O(3), Se, dien, and phen in the presence of transition metals in a methanol solvent under solvothermal conditions. Compounds 1-3 consist of [As(2)Se(6)](2-) anions with [Fe(phen)(3)](2+), [Zn(phen)(dien)](2+), and [{Mn(phen)(2)}(2)(μ-η(2),η(2)-AsSe(4))](+) complex counter cations, respectively. The [As(2)Se(6)](2-) anion is formed from two As(III)Se(3) trigonal pyramids linked through two Se-Se bonds. Compound 3 is the first example of a mixed-valent selenidoarsenate(III,V) and exhibits the coexistence of As(III)Se(3) trigonal pyramidal and As(V)Se(4) tetrahedral units. Compound 4 is composed of a helical chain of [As(2)Se(2)(μ-Se(3))(μ-Se(5))(2-)](∞) and octahedral [Ni(phen)(3)](2+) cations. The [As(2)Se(2)(μ-Se(3))(μ-Se(5))(2-)](∞) chain is constructed from AsSe(+) units alternatively linked by μ-Se(3)(2-) and μ-Se(5)(2-) bridging ligands. When the structures of compounds 1-4 are compared, the transition metal ions show different structural directing effects during the synthesis of arsenic polyselenides in methanol. Compounds 1, 2, 3, and 4 exhibit semiconducting properties with band gaps of 1.88, 2.29, 1.82, and 2.01 eV, respectively.
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