Supramolecular Polymers Based on Planar Organoboranes
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摘要: 超分子聚合物，即单体通过非共价键作用连接而成的链状聚集体，具有独特的物化性质和功能。经过30年的发展，超分子聚合物领域已取得了一系列重大创新成果。目前，超分子聚合物领域亟需探索的问题主要在超分子聚合驱动力、超分子构筑基元、可控超分子聚合、超分子聚合物功能等方面。近期，荷兰埃因霍温理工大学的Meijer课题组和日本名古屋大学的Yamaguchi课题组合作，首次将受阻路易斯酸碱对（FLP）引入到超分子共聚物中，通过发展基于平面三芳基硼和三芳基胺的FLP构筑基元，实现了B−N配位非共价键作用驱动聚合形成超分子聚合物，获得的聚合物具有长寿命和圆偏振特征的光致发光性质。同时，Yamaguchi课题组提出一种新的超分子聚合方法，即基于分子内氢键和分子间B−N配位作用构筑的双重陷阱亚稳态，实现了动态可控的超分子聚合。这些工作发展出新的超分子聚合驱动力和构筑基元，也为超分子聚合提供了新聚合方法，为超分子聚合物的功能化提供了新思路。
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关键词:
- 超分子聚合物 /
- 非共价键作用 /
- 受阻Lewis酸碱对 /
- 有机硼化学
Abstract: Supramolecular polymers, which are chain-like aggregates of monomers connected by noncovalent interactions, possess some unique chemical and physical properties and functions. In the past thirty years, great achievements have been made in the field of supramolecular polymers. So far, there are some critical issues in this research field, including the development of the driving forces and design strategies for supramolecular polymerization, and supramolecular building blocks and functions of supramolecular polymers. Recently, for the first time, Meijer et al in Eindhoven University of Technology and Yamaguchi et al in Nagoya University incorporated the frustrated Lewis pair (FLP) into the design of supramolecular polymers. By developing FLP building blocks based on planar triarylborane and triarylamine, the supramolecular polymers were constructed based on noncovalent interactions of B−N coordination, and these polymers exhibited the unique fluorescence properties with the long lifetime and circularly polarized nature. Furthermore, Yamaguchi et al disclosed a novel supramolecular polymerization method through the design of the double-trap metastable state enabled by intramolecular hydrogen bonds and intermolecular B−N coordination, achieving dynamic and controllable supramolecular polymerization. These studies thus developed new driving forces and building blocks for supramolecular polymerization, and also provided novel design strategies for supramolecular polymerization and new functions of supramolecular polymers. -
图 1 （a）S-B1和S-N1超分子单体结构式; （b） 从单体溶解态经缓慢冷却后的共聚机理示意图; （c） 在长波紫外灯的光激发下，滴涂样品的照片；（d） 20 °C下各超分子聚合物的光致发光光谱 (λex = 400 nm) [5]
Figure 1. （a） Structural formula of S-B1 and S-N1 supramolecular monomers; （b） Schematic diagram of copolymerization mechanism after slow cooling from monomerically dissolved state; （c） The photo of the drop-casted samples under photoexcitation of a long-wavelength UV lamp; （d） Photoluminescence emission spectra of supramolecular polymers （λex = 400 nm; 20 °C） [5]
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