Bimolecular Excited-State Proton-Coupled Electron Transfer within Encounter Complexes

[Image: see text] Bimolecular excited-state proton-coupled electron transfer (PCET*) was observed for reaction of the triplet MLCT state of [(dpab)(2)Ru(4,4′-dhbpy)](2+) (dpab = 4,4′-di(n-propyl)amido-2,2′-bipyridine, 4,4′-dhbpy = 4,4′-dihydroxy-2,2′-bipyridine) with N-methyl-4,4′-bipyridinium (MQ(+)) and N-benzyl-4,4′-bipyridinium (BMQ(+)) in dry acetonitrile solutions. The PCET* reaction products, the oxidized and deprotonated Ru complex, and the reduced protonated MQ(+) can be distinguished from the excited state electron transfer (ET*) and the excited state proton transfer (PT*) products by the difference in the visible absorption spectrum of the species emerging from the encounter complex. The observed behavior differs from that of reaction of the MLCT state of [(bpy)(2)Ru(4,4′-dhbpy)](2+) (bpy = 2,2′-bipyridine) with MQ(+), where initial ET* is followed by diffusion-limited proton transfer from the coordinated 4,4′-dhbpy to MQ(0). The difference in observed behavior can be rationalized based on changes in the free energies of ET* and PT*. Substitution of bpy with dpab results in the ET* process becoming significantly more endergonic and the PT* reaction becoming somewhat less endergonic.