Dynamic Conversion Between Se-N Covalent and Noncovalent Interactions
Dynamic Conversion Between Se-N Covalent and Noncovalent Interactions
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Se-N 共价和非共价相互作用之间的动态转换
DOI：
10.1021/acs.jpca.6b08003
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
Gao Jun
中科院分区：
文献类型：
--
作者：
Xie Meng;Wang LiLi;Liu Fang;Zhang Dongju;Gao Jun
Se-N动态共价键是一种新型的动态共价键，在制备刺激响应性和自愈性功能材料方面具有应用价值。虽然最近在实验方面取得了一些进展，但对Se-N动态共价键的形成机理还知之甚少。本文用密度泛函理论分析了三种吡啶衍生物R-C5H4N[吡啶(R=H)，4-甲基吡啶(R=CH3)，4-二甲氨基-吡啶(R=N(CH3)2)]与苯基硒基溴(PhSeBr)之间的Se-N动态共价键的结构和性质。PhSeBr中的Se原子与吡啶或吡啶衍生物中的N原子之间的相互作用可分为三种模型：解离、非键相互作用和共价键相互作用。对三个系列化合物的量子化学计算表明，这三种模型可以相互转化，导致Se-N动态共价键的产生。在CH2Cl2等极性溶剂中产生的溶剂效应可以使Se-N共价键和Se···N非键相互作用之间的转化变得更容易。吡啶环上取代基的种类会影响转化过程：取代基的给电子能力越强，越容易发生结构转化。
Se–N dynamic covalent bond is a new dynamic covalent bond which has applications in the fabrication of stimuli responsive and self-healing functional materials. Although recent advances have been achieved in the experimental aspect, little is known about the formation mechanism of Se–N dynamic covalent bond. Here the structures and nature of Se–N dynamic covalent bond between three kinds of pyridine derivatives R-C5H4N, [pyridine (R = H), 4-methylpyridine (R = CH3), 4-dimethylamino-pyridine (R = N(CH3)2)] and phenylselenyl bromine (PhSeBr) have been analyzed using density functional theory. The interactions between Se atom in PhSeBr and N atom in pyridine or pyridine derivatives can be divided into three models: dissociation, nonbonding interaction and covalent bond interaction. Quantum chemical calculations on three series compounds show that these three models can convert mutually, which results in the generation of Se–N dynamic covalent bond. Solvent effects produced in polar solvents such as CH2Cl2can make the conversion between Se–N covalent bond and Se···N nonbonding interactions easier. The kind of the substituents in pyridine ring can affect the conversion process: the stronger the electron-donating ability of the substituent, the easier the structure transformation.