The Electron Transfer Process in Mixed Valence Compounds with a Low‐lying Energy Bridge in Different Oxidation States
Yuying Yang, Xiao‐Quan Zhu, Jean‐Pierre Launay, Cheng‐Bin Hong, Shao‐Dong Su, Yuehong Wen, Xin‐Tao Wu, Tian‐Lu Sheng
Abstract
Abstract 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.