Engineering Functionalization in a Supramolecular Polymer: Hierarchical Self-Organization of Triply Orthogonal Non-covalent Interactions on a Supramolecular Coordination Complex Platform
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- 作者：Zhixuan Zhou ; Xuzhou Yan ; Timothy R. Cook ; Manik Lal Saha ; Peter J. Stang
- 刊名：Journal of the American Chemical Society
- 出版年：2016
- 出版时间：January 27, 2016
- 年：2016
- 卷：138
- 期：3
- 页码：806-809
- 全文大小：373K
- ISSN：1520-5126
文摘
Here we present a method for the construction of functionalizable supramolecular polymers by controlling three orthogonal interactions within a single system: (i) coordination-driven self-assembly; (ii) H-bonding; and (iii) host–guest interactions between crown ether and dialkylammonium substrates. Three unique molecules constitute the supramolecular construct, including a 2-ureido-4-pyrimidinone (UPy)-functionalized rigid dipyridyl donor and a complementary organoplatinum(II) acceptor decorated with a crown ether moiety that provide the basis for self-assembly and polymerization. The final host–guest interaction is demonstrated by using one of two dialkylammonium molecules containing fluorophores that bind to the benzo-21-crown-7 (B21C7) groups of the acceptors, providing a spectroscopic handle to evaluate the functionalization. An initial coordination-driven self-assembly yields hexagonal metallacycles with alternating UPy and B21C7 groups at their vertices. The assembly does not interfere with H-bonding between the UPy groups, which link the discrete metallacycles into a supramolecular network, leaving the B21C7 groups free for functionalization via host–guest chemistry. The resultant network results in a cavity-cored metallogel at high concentrations or upon solvent swelling. The light-emitting properties of the dialkylammonium substrates were transferred to the network upon host–guest binding. This method is compatible with any dialkylammonium substrate that does not disrupt coordination nor H-bonding, and thus, the unification of these three orthogonal interactions represents a simple yet highly efficient strategy to obtain supramolecular polymeric materials with desirable functionality.