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.
Keywords: Bell-Evans-Polanyi principle; azepine; dual emission; excited-state aromaticity; photoinduced structural planarization.
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