Excited-State Proton Transfer: From Constrained Systems to “Super” Photoacids to Superfast Proton Transfer

We have used knowledge of the electronic structure of excited states of acids to design molecules that exhibit enhanced excited-state acidity. Such "super" photoacids are the strongest reversible photoacids known and allow the time evolution of proton transfer to be examined in a wide array of organic solvents. This includes breaking/formation of the hydrogen bonds in hundreds of femtoseconds, solvent reorientation and relaxation in picoseconds, proton dissociation, and, finally, diffusion and geminate recombination of the dissociated proton, observed in nanoseconds.