Effects of cis/trans-Configuration and Ligand Substitution of the Cyanidometal Bridge on Metal to Metal Charge Transfer Properties in Mixed Valence Complexes |
| |
| Authors: | Dr. Qing-Dou Xu Dr. Xiao Ma Chen Zeng Dr. Shao-Dong Su Sheng-Min Hu Ying-Ying Huang Prof. Xin-Tao Wu Prof. Tian-Lu Sheng |
| |
| Affiliation: | 1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002 P.R. China;2. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou, Fujian, 350002 P.R. China School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049 P.R. China |
| |
| Abstract: | To investigate the effects of cis/trans-configuration of the cyanidometal bridge and the electron donating ability of the auxiliary ligand on the cyanidometal bridge on metal to metal charge transfer (MMCT) in cyanidometal-bridged mixed valence compounds, two groups of trinuclear cyanidometal-bridged compounds cis/trans-[Cp(dppe)Fe(μ-NC)Ru(4,4’-dmbpy)2(μ-CN)Fe(dppe)Cp][PF6]n (n=2 ( cis/trans - 1[PF6]2 ), 3 ( cis/trans - 1[PF6]3 ), 4 ( cis/trans - 1[PF6]4 )) and cis/trans-[Cp(dppe)Fe(μ-NC)Ru(bpy)2(μ-CN)Fe(dppe)Cp][PF6]3 ( cis/trans - 2[PF6]3 ) were synthesized and fully characterized. The experimental results indicate that for these one- and two-electron oxidation mixed valence compounds, the trans-configuration compounds are more beneficial for MMCT than the cis-configuration compounds, and increasing the electron donating ability of the auxiliary ligand on the cyanidometal bridge is also conductive to MMCT. Moreover, compounds cis/trans - 1[PF6]n (n=3, 4) and cis/trans - 2[PF6]3 belong to localized compounds by analyzing the experimental characterization results, supported by the TDDFT calculations. |
| |
| Keywords: | cis/trans-configuration crystal structure cyanidometal bridge electron transfer mixed valence compounds |
|
|
