Cation- and Anion-Exchanges Induce Multiple Distinct Rearrangements within Metallosupramolecular Architectures

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• 作者：Imogen A. Riddell ; Tanya K. Ronson ; Jack K. Clegg ; Christopher S. Wood ; Rana A. Bilbeisi ; Jonathan R. Nitschke
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：July 2, 2014
• 年：2014
• 卷：136
• 期：26
• 页码：9491-9498
• 全文大小：401K
• ISSN：1520-5126

文摘

Different anionic templates act to give rise to four distinct Cd^II-based architectures: a Cd₂L₃ helicate, a Cd₈L₁₂ distorted cuboid, a Cd₁₀L₁₅ pentagonal prism, and a Cd₁₂L₁₈ hexagonal prism, which respond to both anionic and cationic components. Interconversions between architectures are driven by the addition of anions that bind more strongly within a given product framework. The addition of Fe^II prompted metal exchange and transformation to a Fe₄L₆ tetrahedron or a Fe₁₀L₁₅ pentagonal prism, depending on the anionic templates present. The equilibrium between the Cd₁₂L₁₈ prism and the Cd₂L₃ triple helicate displayed concentration dependence, with higher concentrations favoring the prism. The Cd₁₂L₁₈ structure serves as an intermediate en route to a hexafluoroarsenate-templated Cd₁₀L₁₅ complex, whereby the structural features of the hexagonal prism preorganize the system to form the structurally related pentagonal prism. In addition to the interconversion pathways investigated, we also report the single-crystal X-ray structure of bifluoride encapsulated within a Cd₁₀L₁₅ complex and report solution state data for J-coupling through a CH路路路F^{鈥?/sup> hydrogen bond indicating the strength of these interactions in solution.}