RESUMEN
An amendment to this paper has been published and can be accessed via a link at the top of the paper.
RESUMEN
The original version of this Article contained errors in the symbols displayed in the eighteenth sentence of the third paragraph of the 'Determination of Hab and kET data for the Mo2 dimers' section of the Results, and the third sentence of the Discussion. This has been corrected in both the PDF and HTML versions of the Article.
RESUMEN
Thermal electron transfer through hydrogen bonds remains largely unexplored. Here we report the study of electron transfer through amide-amide hydrogen bonded interfaces in mixed-valence complexes with covalently bonded Mo2 units as the electron donor and acceptor. The rate constants for electron transfer through the dual hydrogen bonds across a distance of 12.5 Å are on the order of â¼ 1010 s-1, as determined by optical analysis based on Marcus-Hush theory and simulation of ν(NH) vibrational band broadening, with the electron transfer efficiencies comparable to that of π conjugated bridges. This work demonstrates that electron transfer across a hydrogen bond may proceed via the known proton-coupled pathway, as well as an overlooked proton-uncoupled pathway that does not involve proton transfer. A mechanistic switch between the two pathways can be achieved by manipulation of the strengths of electronic coupling and hydrogen bonding. The knowledge of the non-proton coupled pathway has shed light on charge and energy transport in biological systems.
