Hu Weilin, Zhang Zhiyun, Xiong Wan, Li Mingyao, Yan Yong, Yang Caiyao, Zou Qi, Lü Jing-Tao, Tian He, Guo Xuefeng
Beijing National Laboratory for Molecular Sciences, National Biomedical Imaging Center, College of Chemistry and Molecular Engineering, Peking University, 292 Chengfu Road, Haidian District, Beijing 100871, P. R. China.
Key Laboratory for Advanced Materials and Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. China.
Sci Adv. 2024 Jul 12;10(28):eado1125. doi: 10.1126/sciadv.ado1125.
Chirality is an important aspect of nature, and numerous macroscopic methods have been developed to understand and control chirality. For the chiral tertiary amines, their flexible flipping process makes it possible to achieve high chiral controllability without bond formation and breaking. Here, we present a type of stable chiral single-molecule devices formed by tertiary amines, using graphene-molecule-graphene single-molecule junctions. These single-molecule devices allow real-time, in situ, and long-time measurements of the flipping process of an individual chiral nitrogen center with high temporal resolution. Temperature- and bias voltage-dependent experiments, along with theoretical investigations, revealed diverse chiral intermediates, indicating the regulation of the flipping dynamics by energy-related factors. Angle-dependent measurements further demonstrated efficient enrichment of chiral states using linearly polarized light by a symmetry-related factor. This approach offers a reliable means for understanding the chirality's origin, elucidating microscopic chirality regulation mechanisms, and aiding in the design of effective drugs.
手性是自然界的一个重要方面，人们已经开发出许多宏观方法来理解和控制手性。对于手性叔胺，其灵活的翻转过程使得在不形成和断裂化学键的情况下实现高的手性可控性成为可能。在此，我们展示了一种由叔胺形成的稳定的手性单分子器件，采用石墨烯-分子-石墨烯单分子结。这些单分子器件允许以高时间分辨率对单个手性氮中心的翻转过程进行实时、原位和长时间测量。温度和偏置电压相关的实验以及理论研究揭示了多种手性中间体，表明能量相关因素对手性翻转动力学的调节作用。角度相关测量进一步证明了利用对称相关因素通过线偏振光对手性态的有效富集。这种方法为理解手性的起源、阐明微观手性调控机制以及辅助有效药物的设计提供了一种可靠的手段。
