The Electron Transfer Process in Mixed Valence Compounds with a Low‐lying Energy Bridge in Different Oxidation States

Mixed‐valence compounds with the iso‐cyanidometal‐ligand bridge in different oxidation states are used as models for the investigation of the electron‐transfer process. We synthesized a series of trimetallic isocyanidometal‐bridged compounds with [Fe–CN–Ru–NC–Fe]n+ (n=2–4), in which the one‐electron...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie International Edition 2021-02, Vol.60 (9), p.4804-4814
Main Authors: Yang, Yu‐Ying, Zhu, Xiao‐Quan, Launay, Jean‐Pierre, Hong, Cheng‐Bin, Su, Shao‐Dong, Wen, Yue‐Hong, Wu, Xin‐Tao, Sheng, Tian‐Lu
Format: Article
Language:English
Subjects:
cyanide complexes
Electron transfer
electron transfer excited state
electron transfer process
Electrons
mixed-valence compounds
Movable bridges
Oxidation
transition metals
Valence
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Mixed‐valence compounds with the iso‐cyanidometal‐ligand bridge in different oxidation states are used as models for the investigation of the electron‐transfer process. We synthesized a series of trimetallic isocyanidometal‐bridged compounds with [Fe–CN–Ru–NC–Fe]n+ (n=2–4), in which the one‐electron oxidation product (N3+) and two‐electron oxidation product (N4+) compounds possess an isocyanidometal bridge whose energy is, respectively lower and slightly higher than the terminal metal centers energies. For the N3+ compounds, the bridge state (FeII–RuIII–FeII) and mixed‐valence states (FeIII–RuII–FeII or FeII–RuII–FeIII) could be simultaneously observed on the IR timescale. For the N4+ compounds, as the donor becomes stronger the electron transfer bridge excited state (FeIII–RuII–FeIII) becomes more and more stable, and even becomes ground state due to the strong electronic coupling between Fe and Ru. For the R+‐B‐R (R is the redox center and B is the bridging ligand) mixed‐valence system with a low‐lying energy bridge, the energy difference (ΔG0) between the bridge state (R‐B+‐R) and mixed‐valence states (R+‐B‐R or R‐B‐R+) could be effectively tuned and even become zero by the fine modification of donor substitution.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202014501