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 language | English |
|---|---|
| Article number | 1531 |
| Number of pages | 10 |
| Journal | Nature Communications |
| Volume | 10 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 4 Apr 2019 |
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Efficient electron transfer across hydrogen bond interfaces by proton-coupled and -uncoupled pathways. / Cheng, Tao; Shen, Dong Xue; Meng, Miao; Mallick, Suman; Cao, Lijiu; Patmore, Nathan J.; Zhang, Hong Li; Zou, Shan Feng; Chen, Huo Wen; Qin, Yi; Wu, Yi Yang; Liu, Chun Y.
In: Nature Communications, Vol. 10, No. 1, 1531, 04.04.2019.Research output: Contribution to journal › Article
TY - JOUR
T1 - Efficient electron transfer across hydrogen bond interfaces by proton-coupled and -uncoupled pathways
AU - Cheng, Tao
AU - Shen, Dong Xue
AU - Meng, Miao
AU - Mallick, Suman
AU - Cao, Lijiu
AU - Patmore, Nathan J.
AU - Zhang, Hong Li
AU - Zou, Shan Feng
AU - Chen, Huo Wen
AU - Qin, Yi
AU - Wu, Yi Yang
AU - Liu, Chun Y.
PY - 2019/4/4
Y1 - 2019/4/4
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85063990770&partnerID=8YFLogxK
U2 - 10.1038/s41467-019-09392-7
DO - 10.1038/s41467-019-09392-7
M3 - Article
C2 - 30948718
AN - SCOPUS:85063990770
VL - 10
JO - Nature Communications
JF - Nature Communications
SN - 2041-1723
IS - 1
M1 - 1531
ER -