Xu Qing-Dou, Ma Xiao, Zeng Chen, Su Shao-Dong, Hu Sheng-Min, Huang Ying-Ying, 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, Fujian, 350002, P.R. China.
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, P.R. China.
Chemistry. 2022 Jun 15;28(34):e202104486. doi: 10.1002/chem.202104486. Epub 2022 May 6.
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) (μ-CN)Fe(dppe)Cp][PF ] (n=2 (cis/trans-1[PF ] ), 3 (cis/trans-1[PF ] ), 4 (cis/trans-1[PF ] )) and cis/trans-[Cp(dppe)Fe(μ-NC)Ru(bpy) (μ-CN)Fe(dppe)Cp][PF ] (cis/trans-2[PF ] ) 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[PF ] (n=3, 4) and cis/trans-2[PF ] belong to localized compounds by analyzing the experimental characterization results, supported by the TDDFT calculations.
为了研究氰基金属桥的顺式/反式构型以及氰基金属桥上辅助配体的给电子能力对氰基金属桥联混合价化合物中金属到金属电荷转移（MMCT）的影响，合成并全面表征了两组三核氰基金属桥联化合物顺式/反式-[Cp(dppe)Fe(μ-NC)Ru(4,4'-dmbpy)(μ-CN)Fe(dppe)Cp][PF₆]（n = 2（顺式/反式-1[PF₆]）、3（顺式/反式-1[PF₆]）、4（顺式/反式-1[PF₆]））和顺式/反式-[Cp(dppe)Fe(μ-NC)Ru(bpy)(μ-CN)Fe(dppe)Cp][PF₆]（顺式/反式-2[PF₆]）。实验结果表明，对于这些单电子和双电子氧化混合价化合物，反式构型化合物比顺式构型化合物更有利于MMCT，并且提高氰基金属桥上辅助配体的给电子能力也有助于MMCT。此外，通过分析实验表征结果并得到TDDFT计算的支持，顺式/反式-1[PF₆]（n = 3, 4）和顺式/反式-2[PF₆]化合物属于定域化合物。
