We have used a series of bifunctional photoacids where the proton is transferred in the excited state from an OH side-group to a basic side group placed on the same aromatic molecule. Our study involves a range of driving forces facilitating relatively long-range through-solvent proton transfer. We find that for proton transfer over a distance greater than 3 water molecules such as in the case of 1-hydroxy-6-carboxypyrene the proton transfer reaction is purely diffusive while over shorter water separation distances between the  acid and base side-groups the reaction may become partially non-diffusive when the driving force is large. We discuss strongly down-hill (in free energy) proton transfer reactions between acid and base using a theory recently developed by Hynes et.al. for proton transfer within water-separated hydrogen-bonding complexes of carbonic acid and a base.

Point to point proton transfer in aqueous solutions

256th National Meeting (2018)

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