Photoinduced Proton and Charge Transfer in 2‑(2′- Hydroxyphenyl)imidazo[4,5‑b]pyridine

This is the peer-reviewed version of the following article: The Journal of Physical Chemistry B 2013, 117, 884–896, DOI: 10.1021/jp311709c, which has been published in final form at https://pubs.acs.org/doi/abs/10.1021/jp311709c. This article may be used for non-commercial purposes onlyThis paper deals with the interplay between solvent properties and isomerism of 2-(2′-hydroxyphenyl)imidazo[4,5-b]pyridine (1), and the proton and charge-transfer processes that the different isomers undergo in the first-excited singlet state. We demonstrate the strong influence of these processes on the fluorescence properties of 1. We studied the behavior of 1 in several neutral and acidified solvents, by UV–vis absorption spectroscopy and by steady-state and time-resolved fluorescence spectroscopy. The fluorescence of 1 showed a strong sensitivity to the environment. This behavior is the result of conformational and isomeric equilibria and the completely different excited-state behavior of the isomers. For both neutral and cationic 1, isomers with intramolecular hydrogen bond between the hydroxyl group and the benzimidazole N undergo an ultrafast excited-state intramolecular proton transfer (ESIPT), yielding tautomeric species with very large Stokes shift. For both neutral and cationic 1, isomers with the OH group hydrogen-bonded to the solvent behave as strong photoacids, dissociating in the excited state in solvents with basic character. The pyridine nitrogen exhibits photobase character, protonating in the excited state even in some neutral solvents. An efficient radiationless deactivation channel of several species was detected, which we attributed to a twisted intramolecular charge-transfer (TICT) process, facilitated by deprotonation of the hydroxyl group and protonation of the pyridine nitrogenThis work has been supported by the Spanish Government and the European Regional Development Fund (Grant CTQ2010-17835) and the Xunta de Galicia (Grant CN 2012/314). A.B., M.V., and J.L.P.L. are thankful for a “Fundación Segundo Gil Dávila” fellowship, a MEC-FPU fellowship, and a “Ramon y Cajal” contract, respectivelyS

Moderately Strong Photoacid Dissociates in Alcohols with High Transient Concentration of the Proton-Transfer Contact Pair

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 onlyProton 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 determinedWe 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 supportS

Dissociation of a Strong Acid in Neat Solvents: Diffusion Is Observed after Reversible Proton Ejection Inside the Solvent Shell

This is the peer-reviewed version of the following article: The Journal of Physical Chemistry B 2013, 117, 14065–14078, DOI: 10.1021/jp4042765, which has been published in final form at https://pubs.acs.org/doi/abs/10.1021/jp4042765. This article may be used for non-commercial purposes onlyStrong-acid dissociation was studied in alcohols. Optical excitation of the cationic photoacid N-methyl-6-hydroxyquinolinium triggers proton transfer to the solvent, which was probed by spectral reconstruction of picosecond fluorescence traces. The process fulfills the classical Eigen–Weller mechanism in two stages: (a) solvent-controlled reversible dissociation inside the solvent shell and (b) barrierless splitting of the encounter complex. This can be appreciated only when fluorescence band integrals are used to monitor the time evolution of the reactant and product concentrations. Band integrals are insensitive to solvent dynamics and report relative concentrations directly. This was demonstrated by first measuring the fluorescence decay of the conjugate base across the full emission band, independently of the proton-transfer reaction. Multiexponential decay curves at single wavelengths result from a dynamic red shift of fluorescence in the course of solvent relaxation, whereas clean single exponential decays are obtained if the band integral is monitored instead. The extent of the shift is consistent with previously reported femtosecond transient absorption measurements, continuum theory of solvatochromism, and molecular properties derived from quantum chemical calculations. In turn, band integrals show clean biexponential decay of the photoacid and triexponential evolution of the conjugate base in the course of the proton transfer to solvent reaction. The dissociation step follows the slowest stage of solvation, which was measured here independently by picosecond fluorescence spectroscopy in five aliphatic alcohols. Also, the rate constant of the encounter-complex splitting stage is compatible with proton diffusion. Thus, for this photoacid, both stages reach the highest possible rates: solvation and diffusion control. Under these conditions, the concentration of the encounter complex is substantial during the earliest nanosecondWe thank the Spanish Government and the European Regional Development Fund (grant nos. CTQ2010-17835, CTQ2010-17026, and CTQ2011-29311-C02-01) and the Xunta de Galicia (grants nos. CN 2012/314, 2012-PG237, GPC2013/052 and INCITE09 314 252 PR) for financial support of our work. J.L.P.L. thanks the Spanish Ministry of Economy and Competitiveness for funding through the Ramon y Cajal ́ Programm 2009. M.V. and C.C.B. thank the Spanish Government for funding through the FPU program. A. B. thanks the Segundo Gil Dávila Foundation for financial supportS