Responsive Supramolecular Polymer Metallogel Constructed by Orthogonal Coordination-Driven Self-Assembly and Host/Guest Interactions

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• 作者：Xuzhou Yan ; Timothy R. Cook ; J. Bryant Pollock ; Peifa Wei ; Yanyan Zhang ; Yihua Yu ; Feihe Huang ; Peter J. Stang
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：March 26, 2014
• 年：2014
• 卷：136
• 期：12
• 页码：4460-4463
• 全文大小：356K
• 年卷期：v.136,no.12(March 26, 2014)
• ISSN：1520-5126

文摘

An emerging strategy for the fabrication of advanced supramolecular materials is the use of hierarchical self-assembly techniques wherein multiple orthogonal interactions between molecular precursors can produce new species with attractive properties. Herein, we unify the spontaneous formation of metal鈥搇igand bonds with the host/guest chemistry of crown ethers to deliver a 3D supramolecular polymer network (SPN). Specifically, we have prepared a highly directional dipyridyl donor decorated with a benzo-21-crown-7 moiety that undergoes coordination-driven self-assembly with a complementary organoplatinum acceptor to furnish hexagonal metallacycles. These hexagons subsequently polymerize into a supramolecular network upon the addition of a bisammonium salt due to the formation of [2]pseudorotaxane linkages between the crown ether and ammonium moieties. At high concentrations, the resulting 3D SPN becomes a gel comprising many cross-linked metallohexagons. Notably, thermo- and cation-induced gel鈥搒ol transitions are found to be completely reversible, reflecting the dynamic and tunable nature of such supramolecular materials. As such, these results demonstrate the structural complexity that can be obtained when carefully controlling multiple interactions in a hierarchical fashion, in this case coordination and host/guest chemistry, and the interesting dynamic properties associated with the materials thus obtained.