Two-Dimensional and Three-Dimensional Coordination Polymers of Hexakis(4-cyanophenyl)[3]radialene: The Role of Stoichiometry and Kinetics

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• 作者：Courtney A. Hollis ; Stuart R. Batten ; Christopher J. Sumby
• 刊名：Crystal Growth & Design
• 出版年：2013
• 出版时间：June 5, 2013
• 年：2013
• 卷：13
• 期：6
• 页码：2350-2361
• 全文大小：761K
• 年卷期：v.13,no.6(June 5, 2013)
• ISSN：1528-7505

文摘

Hexakis(4-cyanophenyl)[3]radialene (1) is a hexadentate ligand that has previously been shown to form isomorphous honeycomb two-dimensional (2-D) coordination polymers {[Ag(1)](X)路2(CH₃NO₂)}_n (X = ClO₄, 2a; X = PF₆, 2b) upon reaction with AgClO₄ and AgPF₆. Within these coordination polymers, close contacts were observed between the anions and the electron-deficient [3]radialene core. Here the synthesis and characterization of four new coordination polymers of 1 and copper(I), {[Cu₂(1)₂](X)₂路Y(CH₃NO₂)}_n (X = BF₄, Y = 20, 4a; X = PF₆, Y = 14, 4b) and {[Cu(1)](X)路2(CH₃NO₂)}_n (X = BF₄, 5a; X = PF₆, 5b), are reported, along with two further examples of the (6,3) network {[Ag(1)](X)路2(CH₃NO₂)}_n (X = BF₄, 2c; X = SbF₆, 2d), and an 8-fold interpenetrated (10,3)-b net formed from 1 and AgClO₄, {[Ag₃(1)](ClO₄)₃路CH₃NO₂}_n (3). Coordination polymers 2a鈥?b>2d were synthesized using low ratios of ligand to metal, 1:1 to 1:3, whereas other examples described herein (compounds 3, 4, and 5) were obtained via the use of a considerably higher ligand-to-metal salt ratio, in the range of 1:6 to 1:18. Reaction of 1 with [Cu(CH₃CN)₄]BF₄ and [Cu(CH₃CN)₄]PF₆ gave isostructural coordination polymers. In each experiment, a three-dimensional (3-D) network with a (4.6²)(4².6)(4³.6⁶.8⁶) topology (4a and 4b) formed first, while a honeycomb two-dimensional (2-D) coordination polymer, with a fully cross-linked bilayer (5a and 5b) crystallized second. Unlike the case for the Ag(I) coordination polymers, the rate of crystallization rather than the stoichiometry of the reactions dictated the structure of the final product for the Cu(I) compounds. The presence of radialene鈥揳nion interactions within these coordination polymers is also discussed, with anion-蟺 interactions being observed to be of lesser significance relative to weak C鈥揌路路路anion hydrogen bonding.