Solvothermal Synthesis and Characterization of Polyselenidoarsenate Salts of Transition Metal Complex Cations
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- 作者：Dingxian Jia ; Jing Zhao ; Yingli Pan ; Weiwei Tang ; Bing Wu ; Yong Zhang
- 刊名：Inorganic Chemistry
- 出版年：2011
- 出版时间：August 1, 2011
- 年：2011
- 卷：50
- 期：15
- 页码：7195-7201
- 全文大小：933K
- 年卷期：v.50,no.15(August 1, 2011)
- ISSN：1520-510X
文摘
The polyselenidoarsenates [Fe(phen)3][As2Se6] (1), [Zn(phen)(dien)][As2Se6]路2phen (2), [{Mn(phen)2}2(渭鈥撐?sup>2,畏2-AsSe4)]2[As2Se6]路H2O (3), and [Ni(phen)3][As2Se2(渭-Se3)(渭-Se5)] (4) (dien = diethylenetriamine and phen = 1,10-phenanthroline) were prepared by the reaction of As2O3, Se, dien, and phen in the presence of transition metals in a methanol solvent under solvothermal conditions. Compounds 1鈥?b>3 consist of [As2Se6]2鈥?/sup> anions with [Fe(phen)3]2+, [Zn(phen)(dien)]2+, and [{Mn(phen)2}2(渭-畏2,畏2-AsSe4)]+ complex counter cations, respectively. The [As2Se6]2鈥?/sup> anion is formed from two AsIIISe3 trigonal pyramids linked through two Se鈥揝e bonds. Compound 3 is the first example of a mixed-valent selenidoarsenate(III,V) and exhibits the coexistence of AsIIISe3 trigonal pyramidal and AsVSe4 tetrahedral units. Compound 4 is composed of a helical chain of [As2Se2(渭-Se3)(渭-Se5)2鈥?/sup>]鈭?/sub> and octahedral [Ni(phen)3]2+ cations. The [As2Se2(渭-Se3)(渭-Se5)2鈥?/sup>]鈭?/sub> chain is constructed from AsSe+ units alternatively linked by 渭-Se32鈥?/sup> and 渭-Se52鈥?/sup> bridging ligands. When the structures of compounds 1鈥?b>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.