Correlated solvent coordinates accelerate multi-donor proton-coupled electron transfer

The rate of charge transfer within a discrete donor-acceptor (D/A) pair is well-described by semi-classical electron transfer theory, but the effects of multiple equivalent redox sites remain less understood. We report a series of ground-state intramolecular proton-coupled electron transfer (PCET) complexes designed to isolate the effects of donor number, <i>N</i>, while holding geometry, coupling, and driving forces constant. The [Ru(L)_3-<i>N</i> (OH) _<i>N</i> ]²⁺ complexes incorporate one, two, or three identical phenolic electron donors linked to Ru through rigid phenanthroline bridges (OH = 2,4-di-<i>tert-</i>butyl-6-(1-methyl-1<i>H</i>-imidazo[4,5-<i>f</i>][1,10]phenanthrolin-2-yl)phenol). Upon flash photolysis and oxidative quenching with methyl viologen (MV²⁺), the transient Ru(iii) oxidizes an appended phenol by PCET with the hydrogen-bonded imidazole nitrogen atom functioning as the base. The rate increased by 3.4-fold and 5.7-fold (1.7-fold and 1.9-fold after statistical correction) for two- and three-donor complexes compared to the single-donor system. The supra-statistical acceleration is attributed to a reduced effective outer sphere reorganization energy (<i>λ</i> _m) modeled by a partially shared solvent reaction coordinate, in which a subset of solvent dipoles is already oriented to stabilize charge from any donor. The final phenoxyl radical state is localized due to the transfer of a proton, and the recombination reaction with the viologen radical is not accelerated. These results demonstrate the effects of solvent dynamics on intramolecular PCET rates, offering a new strategy for the design of synthetic charge transfer systems.