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The Electron Transfer Process in Mixed Valence Compounds with a Low‐lying Energy Bridge in Different Oxidation States
Author(s) -
Yang YuYing,
Zhu XiaoQuan,
Launay JeanPierre,
Hong ChengBin,
Su ShaoDong,
Wen YueHong,
Wu XinTao,
Sheng TianLu
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202014501
Subject(s) - chemistry , valence (chemistry) , electron transfer , excited state , oxidation state , metal , transition metal , crystallography , electronic structure , valence electron , electron , atomic physics , computational chemistry , catalysis , physics , organic chemistry , quantum mechanics , biochemistry
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 ( N 3+ ) and two‐electron oxidation product ( N 4+ ) compounds possess an isocyanidometal bridge whose energy is, respectively lower and slightly higher than the terminal metal centers energies. For the N 3+ compounds, the bridge state (Fe II –Ru III –Fe II ) and mixed‐valence states (Fe III –Ru II –Fe II or Fe II –Ru II –Fe III ) could be simultaneously observed on the IR timescale. For the N 4+ compounds, as the donor becomes stronger the electron transfer bridge excited state (Fe III –Ru II –Fe III ) becomes more and more stable, and even becomes ground state due to the strong electronic coupling between Fe and Ru.