Recent experimental advances on excited-state intramolecular proton coupled electron transfer reaction.

Proton-coupled electron transfer reactions form the basis of many important chemical processes including much of the energy conversion that occurs within living cells. However, much of the physical chemistry that underlies these reaction mechanisms remains poorly understood. In this Account, we report on recent progress in the understanding of excited-state intramolecular proton-coupled electron transfer (PCET) reactions. The strategic design and synthesis of various types of PCET molecules, along with steady-state and femtosecond time-resolved spectroscopy, have uncovered the mechanisms of several excited-state PCET reactions in solution. These experimental advancements correlate well with current theoretical models, in which the proton has quantum motion with a high probability of tunneling. In addition, the rate of proton transfer is commonly incorporated within the rate of rearrangement of solvent molecules. As a result, the reaction activation free energy is essentially governed by the solvent reorganization because the charge redistribution is considered based on a solvent polarity-induced barrier instead of the height of the proton migration barrier. In accord with this theoretical basis, we can rationalize the observation that the proton transfer for many excited-state PCET systems occurs during the solvent relaxation time scale of 1-10 ps: the highly exergonic reaction takes place before the system reaches its equilibrium polarization. Also, we have used various derivatives of proton transfer molecules, especially those of 3-hydroxyflavone to clearly demonstrate how researchers can tune the dynamics of excited-state PCET through changes in the magnitude or direction of the dipole vector within the reaction. Subsequently, using 2-(2'-hydroxyphenyl)benzoxazole as the parent model, we then report on methods for the development of an ideal system for probing PCET reaction. Because future biomedical applications of such systems will likely occur in aqueous environments, we discuss various 7-azaindole analogues, for which proton transfer requires the assistance of protic solvent molecules. These results provide a unique contrast to the ubiquitous studies on the dynamic solvent effects of PCET molecules that undergo intrinsic intramolecular proton motion.