Efficient electron transfer across hydrogen bond interfaces by proton-coupled and -uncoupled pathways

Tao Cheng, Dong Xue Shen, Miao Meng, Suman Mallick, Lijiu Cao, Nathan J. Patmore, Hong Li Zhang, Shan Feng Zou, Huo Wen Chen, Yi Qin, Yi Yang Wu, Chun Y. Liu

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

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 Mo 2 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 ∼ 10 10 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.

Original languageEnglish
Article number1531
Number of pages10
JournalNature Communications
Volume10
Issue number1
DOIs
Publication statusPublished - 4 Apr 2019

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