Empirical and Theoretical Insights into the Structural Features and Host鈥揋uest Chemistry of M8L4 Tube Architectures

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• 作者：Wenjing Meng ; Aaron B. League ; Tanya K. Ronson ; Jack K. Clegg ; William C. Isley ; III ; David Semrouni ; Laura Gagliardi ; Christopher J. Cramer ; Jonathan R. Nitschke
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：March 12, 2014
• 年：2014
• 卷：136
• 期：10
• 页码：3972-3980
• 全文大小：472K
• 年卷期：v.136,no.10(March 12, 2014)
• ISSN：1520-5126

文摘

We demonstrate a general method for the construction of M₈L₄ tubular complexes via subcomponent self-assembly, starting from Cu^I or Ag^I precursors together with suitable elongated tetraamine and 2-formylpyridine subcomponents. The tubular architectures were often observed as equilibrium mixtures of diastereomers having two different point symmetries (D_2d or D₂ D₄) in solution. The equilibria between diastereomers were influenced through variation in ligand length, substituents, metal ion identity, counteranion, and temperature. In the presence of dicyanoaurate(I) and Au^I, the D₄-symmetric hosts were able to bind linear Au(Au(CN)₂)₂^{鈥?/sup> (with two different configurations) as the best-fitting guest. Substitution of dicyanoargentate(I) for dicyanoaurate(I) resulted in the formation of Ag(Au(CN)₂)₂鈥?/sup> as the optimal guest through transmetalation. Density functional theory was employed to elucidate the host鈥揼uest chemistries of the tubes.}