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Broadening the Horizon of the Bell–Evans–Polanyi Principle towards Optically Triggered Structure Planarization
Author(s) -
Chen Yi,
Chang KaiHsin,
Meng FanYi,
Tseng ShengMing,
Chou PiTai
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202015274
Subject(s) - azepine , chemical mechanical planarization , chemistry , substituent , double bond , rotation (mathematics) , stereochemistry , mathematics , polymer chemistry , organic chemistry , geometry , layer (electronics)
Abstract Finding a relationship between kinetics and thermodynamics may be difficult. However, semi‐empirical rules exist to compensate for this shortcoming, among which the Bell–Evans–Polanyi ( B‐E‐P ) principle is an example for reactions involving bond breakage and reformation. We expand the B‐E‐P principle to a new territory by probing photoinduced structure planarization (PISP) of a series of dibenz[ b , f ]azepine derivatives incorporating bent‐to‐planar and rotation motion. The latter involves twisting of the partial double bond character, thereby inducing a barrier that is substituent dependent at the para N ‐phenyl position. The transition‐state structure and frequency data satisfy and broaden the B‐E‐P principle to PISP reactions without bond rearrangement. Together with dual emissions during PISP, this makes possible harnessing of the kinetics/thermodynamics relationship and hence ratiometric luminescence properties for excited‐state structural transformations.