From {AuI路路路AuI}-Coupled Cages to the Cage-Built 2-D {AuI路路路AuI} Arrays: AuI路路路AuI Bonding Interaction Driven Self-Assembly and Their

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• 作者：Xuan-Feng Jiang ; Franky Ka-Wah Hau ; Qing-Fu Sun ; Shu-Yan Yu ; Vivian Wing-Wah Yam
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：August 6, 2014
• 年：2014
• 卷：136
• 期：31
• 页码：10921-10929
• 全文大小：618K
• ISSN：1520-5126

文摘

Metal鈥搈etal bonding interactions have been used to generate a number of unique supramolecular assemblies with fascinating functions. We presented here a new class of gold(I)-containing metallosupramolecular cages and cage-built two-dimensional (2-D) arrays of {Au₈L₂}_n (n = 1 or 鈭? L = tetrakis-dithiocarbamato-calix[4]arene, TDCC), 1鈥?b>3, which are constructed from the self-assembly of deep-cavitand calix[4]arene-based supramolecular cages consisting of octanuclear Au(I) motifs. Synchrotron radiation X-ray diffraction structural analyses of 1鈥?b>3 revealed their quadruple-stranded helicate dimeric cage structure and the presence of 2-D arrays of cages linked together by inter- and intramolecular Au^I路路路Au^I interactions. Electronic absorption and emission studies of complexes 1鈥?b>3 indicated the occurrence of a programmable self-assembly process in a concentration-dependent stepwise manner with the links built via aurophilic interactions. These novel gold(I) supramolecular cages exhibited green phosphorescence and have been shown to serve as highly selective proof-of-concept luminescent sensors toward Ag^I cation among various competitive transition-metal ions.