Yang Yu-Ying, Zhu Xiao-Quan, Launay Jean-Pierre, Hong Cheng-Bin, Su Shao-Dong, Wen Yue-Hong, Wu Xin-Tao, Sheng Tian-Lu
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, 350002, Fujian, China.
School of Chemical Sciences, University of Chinese Academy of Sciences, 100049, Beijing, China.
Angew Chem Int Ed Engl. 2021 Feb 23;60(9):4804-4814. doi: 10.1002/anie.202014501. Epub 2021 Jan 15.
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=2-4), in which the one-electron oxidation product (N ) and two-electron oxidation product (N ) compounds possess an isocyanidometal bridge whose energy is, respectively lower and slightly higher than the terminal metal centers energies. For the N compounds, the bridge state (Fe -Ru -Fe ) and mixed-valence states (Fe -Ru -Fe or Fe -Ru -Fe ) could be simultaneously observed on the IR timescale. For the N compounds, as the donor becomes stronger the electron transfer bridge excited state (Fe -Ru -Fe ) becomes more and more stable, and even becomes ground state due to the strong electronic coupling between Fe and Ru.
具有处于不同氧化态的异氰基金属配体桥的混合价化合物被用作研究电子转移过程的模型。我们合成了一系列具有[Fe-CN-Ru-NC-Fe]（n = 2 - 4）的三金属异氰基金属桥连化合物，其中单电子氧化产物（N）和双电子氧化产物（N）化合物拥有一个异氰基金属桥，其能量分别低于和略高于末端金属中心的能量。对于N化合物，在红外时间尺度上可以同时观察到桥态（Fe -Ru -Fe ）和混合价态（Fe -Ru -Fe 或Fe -Ru -Fe ）。对于N化合物，随着供体变得更强，电子转移桥激发态（Fe -Ru -Fe ）变得越来越稳定，并且由于Fe和Ru之间的强电子耦合甚至变为基态。
