Varied forms of lamellar [Sn3Se7]n2n- anion: The competitive and synergistic structure-directing effects of metal-amine complex and imidazolium cations

Cheng Feng Du, Jian Rong Li, Mei Ling Feng, Guo Dong Zou, Nan Nan Shen, Xiao Ying Huang

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摘要

Presented are the syntheses, characterizations and properties of a series of selenidostannate compounds directed by metal-amine complex (MAC) cations and/or [Bmmim]+ (Bmmim = 1-butyl-2,3-dimethylimidazolium). Mixtures of the ionic liquid (IL) (Bmmim)Cl and amines, such as ethylenediamine (en) and diethylenetriamine (dien), in various ratios were used to ionothermally/solvothermally prepare four selenidostannates, namely, [Mn(en)3]Sn3Se7 (1), [Mn(dien)2]Sn3Se7·H2O (2), (Bmmim)3[Mn(en)3]2[Sn9Se21]Cl (3) and (Bmmim)6[Mn(dien)2]2Sn15Se35 (4). Single-crystal X-ray diffraction analyses revealed that these compounds exhibit lamellar anionic [Sn3Se7]n2n- structures. [Sn3Se7]n2n- layers in all 1-4 possess a {63} net, considering [Sn3Se10] semi-cube unit as a 3-connected node; however, diverse multi-membered rings exist there. In compounds 1 and 2, all the [Sn3Se10] units are 3-connected nodes interlinking with each other via edge-sharing two Se atoms to produce six-membered rings. However, in compound 3, the insertion of two [Sn3Se9] units into a six-membered ring results in a novel eight-membered heart-shaped ring, which has never been observed before in the family of chalcogenidostannates. More interestingly, the [Sn3Se7]n2n- layer in compound 4 consists of mixed six- and eight-membered rings. The phase composition is strongly dependent on the ratio of IL to MAC in the syntheses, e.g., 1 and 2 were obtained with IL : MAC ratios less than 3 : 1 and 4 : 1, while 3 and 4 were obtained when the ratios were increased to 4 : 1 and 5 : 1, respectively. The structural variation from 1 to 4 clearly indicates the competitive and synergistic effects between MAC and IL cation on the formation of lamellar selenidostannates. A synthetic approach via varying the ratio of IL to MAC cation as solvent and structure-directing agent will be attractive in the synthesis of novel chalcogenidometallates.

源语言英语
页(从-至)7364-7372
页数9
期刊Dalton Transactions
44
16
DOI
出版状态已出版 - 28 4月 2015
已对外发布

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