Clusters [Co(As3S3)2]2鈥?/sup>, [Ni(As3S3)2]2鈥?/sup>, and [{Co(en)}6(渭3-S)4(AsS3)
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- 作者：Chunying Tang ; Fang Wang ; Wenqing Jiang ; Yong Zhang ; Dingxian Jia
- 刊名：Inorganic Chemistry
- 出版年：2013
- 出版时间：October 7, 2013
- 年：2013
- 卷：52
- 期：19
- 页码：10860-10868
- 全文大小：490K
- 年卷期：v.52,no.19(October 7, 2013)
- ISSN：1520-510X
文摘
Solvothermal reactions of As2O3 and S with CoCl2路6H2O or NiCl2路6H2O in an aqueous solution of dien produced novel thioarsenates [Co(dien)2][Co(As3S3)2] (1) and [Ni(dien)2][Ni(As3S3)2] (2) (dien = diethylenetriamine), and the reaction with CoCl2路6H2O in an aqueous solution of en afforded complex [Hen]2[{Co(en)}6(渭3-S)4(AsS3)4] (3) (en = ethylenediamine). In 1 and 2, one transition-metal ion is coordinated by two dien ligands to form [TM(dien)2]2+ (TM = Co, Ni) complex cations. The As3S3 unit coordinates to the other TM(II) ion with both As- and S-donor atoms to form the [TM(As3S3)2]2鈥?/sup> anionic cluster, in which TMAs2, TMAs2S2, and TMAs3S2 rings are formed. In 3, each Co3+ ion is coordinated by an en ligand. Six Co(en) units are interlinked by four 渭3-S and four AsS3 ligands to form a [{Co(en)}6(渭3-S)4(AsS3)4]2鈥?/sup> cluster containing an adamantane-like Co6S4 core. The AsS3 unit coordinates to Co atom in the 畏1-As1,畏2-S coordination mode with As binding Co(1) and S(1) binding Co(1) and Co(2). The As3S3 and AsS3 ligands with both As- and S-donor atoms in 1鈥?b>3 have never been obtained in amine solution before. The same reactions in pure dien and en solvents afforded compounds [Co(dien)2]3[As3S6]2 (4) and [Co(en)3]2As2S5 (5) containing discrete anions [As3S6]3鈥?/sup> and [As2S5]4鈥?/sup>, respectively. The band gaps of 1鈥?b>3 are in the range of 1.37鈥?.55 eV, and the band gaps of 4 and 5 are 2.24 and 2.26 eV, which show the influence of the coordination mode of thioarsenate ligands on the electronic transitions in the TM-thioarsenates.