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异常卤素-卤素相互作用辅助径向生色团组装。

Anomalous Halogen-Halogen Interaction Assists Radial Chromophoric Assembly.

机构信息

School of Chemistry , Indian Institute of Science Education and Research Thiruvananthapuram , Vithura, Thiruvananthapuram , Kerala , India 695551.

出版信息

J Am Chem Soc. 2019 Mar 20;141(11):4536-4540. doi: 10.1021/jacs.8b13754. Epub 2019 Feb 14.

Abstract

The design of highly efficient supramolecular architectures that mimic competent natural systems requires a comprehensive knowledge of noncovalent interactions. Halogen bonding is an excellent noncovalent interaction that forms halogen-halogen (X) as well as trihalogen interacting synthons. Herein, we report the first observation of a symmetric radial assembly of chromophores ( R3̅ c space group) composed of a stable hexabromine interacting synthon (Br) that further push the limits of our understanding on the nature, role, and potential of noncovalent halogen bonding. Contrary to the destabilization proposed for Type-I X interactions, Br-synthon-possessing Type-I X interactions exhibit a stabilizing nature owing to the exchange-correlation component. The radial assembly of chromophores is further strengthened by intermolecular through-space charge transfer interaction. Br-synthon-driven 3-fold symmetric radial assembly render a lattice structure that reminisces the chromophoric arrangement in the light harvesting system 2 of purple bacteria.

摘要

设计能够模拟高效自然体系的超分子结构需要对非共价相互作用有全面的了解。卤键是一种极好的非共价相互作用,它可以形成卤-卤(X)以及三卤相互作用的构筑基元。在此,我们首次观察到由稳定的六溴相互作用构筑基元(Br)组成的发色团的对称径向组装(R3̅c 空间群),这进一步推动了我们对非共价卤键的本质、作用和潜力的理解。与预期的第一类 X 型相互作用的去稳定化相反,具有第一类 X 型相互作用的 Br 构筑基元表现出稳定的性质,这是由于交换相关分量的存在。发色团的径向组装进一步通过分子间的通过空间电荷转移相互作用得到加强。由 Br 构筑基元驱动的 3 重对称的径向组装使得晶格结构类似于紫色细菌的光捕获系统 2 中的发色团排列。

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