title: Excited-State Proton Transfer in Indigo.
abstract: Excited-state proton transfer (ESPT) in Indigo and its monohexyl-substituted derivative (Ind and NHxInd, respectively) in solution was investigated experimentally as a function of solvent viscosity, polarity, and temperature, and theoretically by time-dependent density functional theory (TDDFT) calculations. Although a single emission band is observed, the fluorescence decays (collected at different wavelengths along the emission band using time-correlated single photon counting (TCSPC)) are biexponential, with two identical decay times but different pre-exponential factors, which is consistent with the existence of excited-state keto and enol species. The femtosecond (fs)-transient absorption data show that two similar decay components are present, in addition to a shorter (<3 ps) component associated with vibrational relaxation. From TDDFT calculations it was shown that with both Ind and NHxInd, the reaction proceeds through a single ESPT mechanism driven by an Arrhenius-type activation through a saddle point, which is enhanced by tunneling through the barrier. From the temperature dependence of the steady-state and time-resolved fluorescence data, the activation energy for the process was found to be ∼11 kJ mol-1for Ind and ∼5 kJ mol-1for NHxInd, in close agreement with the values calculated by TDDFT: 12.3 kJ mol-1(Ind) and 3.1 kJ mol-1(NHxInd). From time-resolved data, the rate constants for the ESPT process in dimethyl sulfoxide were found to be 9.24 × 1010s-1(Ind) and 7.12 × 1010s-1(NHxInd). The proximity between the two values suggests that the proton transfer mechanism in indigo is very similar to that found in NHxInd, where a single proton is involved. In addition, with NHxInd, the TDDFT calculations, together with the viscosity dependence of the fast component, and differences in the activation energy values between the steady-state and time-resolved data indicate that an additional nonradiative process is involved, which competes with ESPT. This is attributed to rotation about the central carbon-carbon bond, which brings the system close to a conical intersection (CI). The CI is of the sloped type, where the seam is reached through an OH stretching vibration.
authors.affiliation: CQC, Department of Chemistry, University of Coimbra , 3004-535 Coimbra, Portugal.
authors.forename: J
authors.initials: J
authors.lastname: Pina
authors.affiliation: CQC, Department of Chemistry, University of Coimbra , 3004-535 Coimbra, Portugal.
authors.forename: Daniela
authors.initials: D
authors.lastname: Sarmento
authors.affiliation: CQC, Department of Chemistry, University of Coimbra , 3004-535 Coimbra, Portugal.|Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia , Via Elce di Sotto, 8, 06123 Perugia, Italia.
authors.forename: Marco
authors.initials: M
authors.lastname: Accoto
authors.affiliation: Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia , Via Elce di Sotto, 8, 06123 Perugia, Italia.
authors.forename: Pier Luigi
authors.initials: PL
authors.lastname: Gentili
authors.affiliation: Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia , Via Elce di Sotto, 8, 06123 Perugia, Italia.
authors.forename: Luigi
authors.initials: L
authors.lastname: Vaccaro
authors.affiliation: Centro de Química Estrutural, Instituto Superior Técnico (IST), Universidade de Lisboa , 1049-001 Lisboa, Portugal.
authors.forename: Adelino
authors.initials: A
authors.lastname: Galvão
authors.affiliation: CQC, Department of Chemistry, University of Coimbra , 3004-535 Coimbra, Portugal.
authors.forename: J Sérgio
authors.identifier: 0000-0001-9708-5079
authors.initials: JS
authors.lastname: Seixas de Melo