Moderately Strong Photoacid Dissociates in Alcohols with High Transient Concentration of the Proton-Transfer Contact Pair
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Title: | Moderately Strong Photoacid Dissociates in Alcohols with High Transient Concentration of the Proton-Transfer Contact Pair |
Author: | Brenlla, Alfonso Veiga Gutiérrez, Manoel Ríos Rodríguez, M. Carmen Rodríguez-Prieto, Flor Mosquera González, Manuel Pérez Lustres, José Luis |
Affiliation: | Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares Universidade de Santiago de Compostela. Departamento de Química Física |
Subject: | Acids and bases | Fluorescence spectroscopy | Kinetics and photochemistry | Proton transfer | Solution chemistry | Time-resolved spectroscopy | |
Date of Issue: | 2014 |
Publisher: | American Chemical Society |
Citation: | Brenlla, A., Veiga Gutiérrez, M., Ríos Rodríguez, M., Rodríguez-Prieto, F., Mosquera, M., & Pérez Lustres, J. (2014). Moderately Strong Photoacid Dissociates in Alcohols with High Transient Concentration of the Proton-Transfer Contact Pair. The Journal Of Physical Chemistry Letters, 5(6), 989-994. doi: 10.1021/jz5001648 |
Abstract: | Proton transfer from strong photoacids to hydroxylic solvents is much under debate. Experimentally, the main issue stems from relaxation and diffusion processes that are concomitant with ultrafast proton transfer and blur population dynamics. To overcome this, we propose a fast photodissociation reaction that, however, proceeds slower than solvent relaxation. Fluorescence spectroscopy of the cationic photoacid 2-(1′-hydroxy-2′-naphtyl)benzimidazolium reveals a two-stage mechanism: (a) reversible elementary proton transfer inside the solvent shell and (b) irreversible contact-pair splitting. The time evolution of the fluorescence signal is complex, yet this is explained quantitatively by simultaneous, spectrally overlapping emission of the acid, the conjugate base, and the contact proton-transfer pair. The latter attains high transient concentration in linear alcohols. Microscopic rate constants of dissociation are determined |
Description: | This is the peer-reviewed version of the following article:
The Journal of Physical Chemistry Letters 2014, 5, 989–994, DOI: 10.1021/jz5001648, which has been published in final form at https://pubs.acs.org/doi/abs/10.1021/jz5001648.
This article may be used for non-commercial purposes only |
Publisher version: | https://doi.org/10.1021/jz5001648 |
URI: | http://hdl.handle.net/10347/17051 |
DOI: | 10.1021/jz5001648 |
E-ISSN: | 1948-7185 |
Rights: | © 2014 American Chemical Society |
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