title: Computational Insights into Excited-State Proton-Transfer Reactions in Azo and Azomethine Dyes.
abstract: 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.
authors.affiliation: CompuNet, Istituto Italiano di Tecnologia, Via Morego 30, 16163, Genoa, Italy. marika.savarese@iit.it.
authors.forename: Marika
authors.initials: M
authors.lastname: Savarese
authors.affiliation: CompuNet, Istituto Italiano di Tecnologia, Via Morego 30, 16163, Genoa, Italy.
authors.forename: Éric
authors.initials: É
authors.lastname: Brémond
authors.affiliation: Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev str., bl. 9, 1113, Sofia, Bulgaria.
authors.forename: Liudmil
authors.initials: L
authors.lastname: Antonov
authors.affiliation: PSL Research University, Institut de Recherche de Chimie Paris IRCP, CNRS-Chimie ParisTech, 11 rue Pierre et Marie Curie, 75005, Paris, France.
authors.forename: Ilaria
authors.initials: I
authors.lastname: Ciofini
authors.affiliation: CompuNet, Istituto Italiano di Tecnologia, Via Morego 30, 16163, Genoa, Italy. carlo.adamo@chimie-paristech.fr.|PSL Research University, Institut de Recherche de Chimie Paris IRCP, CNRS-Chimie ParisTech, 11 rue Pierre et Marie Curie, 75005, Paris, France. carlo.adamo@chimie-paristech.fr.|Institut Universitaire de France, 103 Boulevard Saint Michel, 75005, Paris, France. carlo.adamo@chimie-paristech.fr.
authors.forename: Carlo
authors.initials: C
authors.lastname: Adamo
keywords: charge transfer; density functional calculations; excited-state proton-transfer reactions; photophysics; tautomerism