PAs3S3 Cage as a New Building Block in Copper Halide Coordination Polymers

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• 作者：Patrick Schwarz ; Joachim Wachter ; Manfred Zabel
• 刊名：Inorganic Chemistry
• 出版年：2011
• 出版时间：September 5, 2011
• 年：2011
• 卷：50
• 期：17
• 页码：8477-8483
• 全文大小：1001K
• 年卷期：v.50,no.17(September 5, 2011)
• ISSN：1520-510X

文摘

First examples of the coordination chemistry of the PAs₃S₃ cage were obtained from solutions of PAs₃S₃路W(CO)₅ (1) in CH₂Cl₂ or CH₂Cl₂/toluene and CuX (X = Cl, Br, I) in MeCN through interdiffusion techniques. Crystals of [Cu(PAs₃S₃)₄]X (2, X = Cl; 3, X = Br) and [(Cu₂I)(PAs₃S₃)₃]I (4) were obtained and characterized by Raman spectroscopy (2) and single-crystal X-ray crystallography. The solid-state structures reveal an unexpected coordination versatility of the PAs₃S₃ ligand: apical phosphorus and bridging sulfur atoms interact with copper, while As路路路X interactions determine the dimensionality of the frameworks. The structures of 2 and 3 contain tetrahedral [(PAs₃S₃)₄Cu]⁺ cations as secondary building units (SBUs), which are arranged by interactions with Cl^{鈥?/sup> or Br鈥?/sup> anions into two- and three-dimensional substructures. These interpenetrate into a (2D + 3D) polycatenane. Compound 4 is built up by a one-dimensional [(Cu₂I)(PAs₃S₃)₃]_nn+ ribbon with PAs₃S₃ cages as P,S-linkers. The As atoms of the exo PAs₃S₄ linkers interact with iodide counterions (3.35 < d(As鈥揑) < 3.59 脜). The resulting two-dimensional layer is organized by weak As路路路I interactions (d(As鈥揑 = 3.87 脜) into a 3D network.}