烷基亚胺光驱动分子转动马达的反应机理研究
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- 英文论文题名：The Working Mechanism for Light-Driven Imine Motors
- 论文作者：李苑莹 ; 刘峰毅 ; 王文亮
- 英文论文作者：Yuanying Li ; Fengyi Liu ; Wenliang Wang ; Key Laboratory for Macromolecular Science of Shaanxi Province ; School of Chemistry &Chemical Engineering ; University
- 年：2016
- 作者机构：陕西省大分子科学重点实验室陕西师范大学化学化工学院;
- 论文关键词：分子马达 ; 光异构化 ; 亚胺
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第十八分会：电子结构理论方法的发展与应用
- 语种：中文
- 分类号：O641
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十八分会 ; 电子结构理论方法的发展与应用
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：447k
- 原文格式：D
- 会议级别：全国
摘要
本文采用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)方法研究了Gerb和Lehn~([1])实验上合成的两个以C=N双键为转轴的亚胺分子马达(1,2,见图1)的工作机理。这两个马达由C=N双键的旋转,N反转和定子环反转等机理分别实现两步(马达1)或四步(马达2)的循环运动过程。其光异构化过程均为(n,π*)旋转机制;而基态热螺旋转换存在N反转(24.8kcal·mol~(-1),马达1)和定子环反转(20.0kcal·mol~(-1),马达1)具有两种竞争的过程,可能会对该类体系应用于单向旋转马达造成不利影响。
The DFT and TDDFT methods were employed to investigate the photo-induced and thermal isomerization mechanism of N-alkyl imines rotary motor featuring a C=N axis.The overall reactions include excited-state C=N rotation taking place in(n,π*) PES, ground-state N inversion as well as ring inversion of stators.The N-inversion and ring-inversion were found to be competitive paths with comparable activation barriers, which may be an obstacle for imines to be used as unidirectional rotary motors.
The DFT and TDDFT methods were employed to investigate the photo-induced and thermal isomerization mechanism of N-alkyl imines rotary motor featuring a C=N axis.The overall reactions include excited-state C=N rotation taking place in(n,π*) PES, ground-state N inversion as well as ring inversion of stators.The N-inversion and ring-inversion were found to be competitive paths with comparable activation barriers, which may be an obstacle for imines to be used as unidirectional rotary motors.
引文
[1]Greb L.;Lehn J.M.J.Am.Chem.Soc.2014,136(38):13114.