RT Journal Article
T1 Moderately Strong Photoacid Dissociates in Alcohols with High Transient Concentration of the Proton-Transfer Contact Pair
A1 Brenlla, Alfonso
A1 Veiga Gutiérrez, Manoel
A1 Ríos Rodríguez, María del Carmen
A1 Rodríguez-Prieto, Flor
A1 Mosquera González, Manuel
A1 Pérez Lustres, José Luis
K1 Acids and bases
K1 Fluorescence spectroscopy
K1 Kinetics and photochemistry
K1 Proton transfer
K1 Solution chemistry
K1 Time-resolved spectroscopy
AB 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
PB American Chemical Society
YR 2014
FD 2014
LK http://hdl.handle.net/10347/17051
UL http://hdl.handle.net/10347/17051
LA eng
NO 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
NO 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
NO We thank the Spanish Government and the European Regional Development Fund (Grants CTQ2010-17835 and CTQ2010-17026) and the Xunta de Galicia (Grants CN 2012/314,EM2012/091, and GPC2013/052) for financial support of our work. J.L.P.L. thanks the Spanish Ministry of Economy and Competitiveness for funding through the Ramón y Cajal Programm 2009. M.V.G. and A.B. thank the Spanish Government and the “Segundo Gil-Dávila” Foundation, respectively, for financial support
DS Minerva
RD 22 abr 2026