期刊
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 6, 期 4, 页码 599-604出版社
AMER CHEMICAL SOC
DOI: 10.1021/jz502644h
关键词
-
类别
资金
- French Agence Nationale de la Recherche (ANR) [ANR-11-JS04-0010]
- High-Performance Computing center (pole HPC) at Universite de Strasbourg
- Spanish Secretaria de Estado de Investigacion Desarrollo e Innovacion [CTQ-2012-36966]
- University of Alcala [CCG2013/EXP-089]
- Italian MIUR
- EU [Marie-Curie PIOF-GA-2012-332233]
- National Science Foundation [CHE-1152070]
- Human Frontier Science Program Organization [RGP0049/2012CHE09-56776]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1152070] Funding Source: National Science Foundation
- Agence Nationale de la Recherche (ANR) [ANR-11-JS04-0010] Funding Source: Agence Nationale de la Recherche (ANR)
In light-driven single-molecule rotary motors, the photoisomerization of a double bond converts light energy into the rotation of a moiety (the rotor) with respect to another (the stator). However, at the level of a molecular population, an effective rotary motion can only be achieved if a large majority of the rotors rotate in the same, specific direction. Here we present a quantitative investigation of the directionality (clockwise vs counterclockwise) induced by a single stereogenic center placed in allylic position with respect to the reactive double bond of a model of the biomimetic indanylidene-pyrrolinium framework. By computing ensembles of non-adiabatic trajectories at 300 K, we predict that the photoisomerization is >70% unidirectional for the Z -> E and E -> Z conversions. Most importantly, we show that such directionality, resulting from the asymmetry of the excited state force field, can still be observed in the presence of a small (ca. 2 degrees) pretwist or helicity of the reactive double bond. This questions the validity of the conjecture that a significant double-bond pretwist (e.g., >10 degrees)w in the ground state equilibrium structure of synthetic or natural rotary motors would be required for unidirectional motion.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据