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Atomically Precise Engineering of Single‐Molecule Stereoelectronic Effect
Author(s) -
Meng Linan,
Xin Na,
Wang Jinying,
Xu Jiyu,
Ren Shizhao,
Yan Zhuang,
Zhang Miao,
Shen Cheng,
Zhang Guangyu,
Guo Xuefeng,
Meng Sheng
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202100168
Subject(s) - azobenzene , terphenyl , molecule , dihedral angle , isomerization , ring (chemistry) , molecular switch , chemistry , charge (physics) , crystallography , materials science , chemical physics , stereochemistry , physics , quantum mechanics , hydrogen bond , organic chemistry , catalysis , biochemistry
Charge transport in a single‐molecule junction is extraordinarily sensitive to both the internal electronic structure of a molecule and its microscopic environment. Two distinct conductance states of a prototype terphenyl molecule are observed, which correspond to the bistability of outer phenyl rings at each end. An azobenzene unit is intentionally introduced through atomically precise side‐functionalization at the central ring of the terphenyl, which is reversibly isomerized between trans and cis forms by either electric or optical stimuli. Both experiment and theory demonstrate that the azobenzene side‐group delicately modulates charge transport in the backbone via a single‐molecule stereoelectronic effect. We reveal that the dihedral angle between the central and outer phenyl ring, as well as the corresponding rotation barrier, is subtly controlled by isomerization, while the behaviors of the phenyl ring away from the azobenzene are hardly affected. This tunability offers a new route to precisely engineer multiconfigurational single‐molecule memories, switches, and sensors.