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Computational Insights into Excited‐State Proton‐Transfer Reactions in Azo and Azomethine Dyes
Author(s) -
Savarese Marika,
Brémond Éric,
Antonov Liudmil,
Ciofini Ilaria,
Adamo Carlo
Publication year - 2015
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201500589
Subject(s) - tautomer , intramolecular force , chemistry , excited state , density functional theory , photochemistry , hydrogen bond , fluorescence , proton , ground state , excitation , computational chemistry , molecule , chemical physics , stereochemistry , atomic physics , organic chemistry , physics , quantum mechanics , electrical engineering , engineering
State of the art density functional theory approaches are employed to provide an accurate description of the photophysical properties of azodyes and Schiff bases displaying intramolecular hydrogen‐bonding features. These compounds exist as tautomeric mixtures at the ground state and, in the case of Schiff bases, an excited‐state intramolecular proton transfer (ESIPT) occurs upon excitation. The experimentally observed photophysical properties are discussed here in light of the theoretical findings. To rationalize the different experimentally observed radiative behavior of the azo and azomethine structures, a nonradiative decay pathway that is possibly active in such systems is determined. The characterization of this deactivation path, tested for two related compounds exhibiting different fluorescence quantum yields, enables us to disentangle the different and contrasting effects governing the excited‐state behavior of these molecular systems.