Chen Hang, Tang Xiao, Ye Hebo, Wang Xinchang, Zheng Hao, Hai Yu, Cao Xiaoyu, You Lei
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China.
College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005,China.
Org Lett. 2021 Jan 1;23(1):231-235. doi: 10.1021/acs.orglett.0c03969. Epub 2020 Dec 22.
The role of n → π* orbital interactions in the rotational pathway and barrier of biaryl-based molecular rotors was elucidated through a combined experimental and computational study. The n → π* interaction in the transition state can lead to the acceleration of rotors. The competition between the n → π* interaction and hydrogen bonding further enabled the reversal of the pathway and greasing/braking the rotor in response to acid/base stimuli, thereby creating a switchable molecular rotor.
通过实验和计算相结合的研究，阐明了n→π轨道相互作用在基于联芳基的分子转子的旋转途径和势垒中的作用。过渡态中的n→π相互作用可导致转子加速。n→π*相互作用与氢键之间的竞争进一步使得旋转途径发生反转，并能响应酸碱刺激对转子进行润滑/制动，从而创造出一种可切换的分子转子。
