Influence of the Substitution of the Ligand on MM′CT Properties of Mixed Valence Heterometallic Cyanido-Bridged Ru–Fe Complexes,Crystal Growth & Design

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Influence of the Substitution of the Ligand on MM′CT Properties of Mixed Valence Heterometallic Cyanido-Bridged Ru–Fe Complexes
Crystal Growth & Design ( IF 3.2 ) Pub Date : 2018-04-30 00:00:00 , DOI: 10.1021/acs.cgd.8b00469
Lin-Tao Zhang _{1,

2} , Xiao-Qun Zhu ₁ , Shao-Dong Su _{1,

2} , Yu-Ying Yang _{1,

2} , Sheng-Min Hu ₁ , Yue-Hong Wen ₁ , Xin-Tao Wu ₁ , Tian-Lu Sheng ₁

Affiliation

We investigated how substitution of the ligand around the lower valent metal ion influences the electron transfer properties from the lower valent metal ion to the higher valent metal ion in heterometallic complexes. A series of new binuclear cyanido-bridged Ru/Fe complexes [TpmRu(L)(μ-CN)Fe(dppe)Cp][PF₆]_n (n = 2, 3) (Tpm = Tris(1-pyrazolyl)methane, dppe = bis(diphenylphosphino)ethane, L = 1,10-phenanthroline (phen), 2,2′-bipyridine (bpy), 4,4′-dimethyl-2,2′-bipyridine (4,4′-(CH₃)₂-bpy)) were synthesized and characterized. In the one-electron oxidized [TpmRu^II(L)(μ-CN)Fe^III(dppe)Cp][PF6]₃ binuclear system, the cyanide bridge promotes the electron transfer from the Ru^II ion to the Fe^III ion. As the substitution of L changes from 1,10-phenanthroline to 4,4′-dimethyl-2,2′-bipyridine, their molecular structure, cyclic voltammetry, IR and UV present obvious changing trends. Moreover, the assignment of MM′CT transition and the differences of electronic properties in the different mixed complexes with different L ligands can be reasonably elucidated via time-dependent density functional theory/density functional theory calculations.

中文翻译：

配体的取代对价态杂金属氰基桥联Ru-Fe配合物MM'CT性质的影响

我们研究了低价金属离子周围配体的取代如何影响杂金属络合物中从低价金属离子到高价金属离子的电子转移性质。一系列新的双核氰基桥联Ru / Fe络合物[TpmRu（L）（μ-CN）Fe（dppe）Cp] [PF ₆ ] _n（n = 2，3）（Tpm =三（1-吡唑基）甲烷，dppe =双（二苯基膦基）乙烷，L = 1,10-菲咯啉（phen），2,2'-联吡啶（bpy），4,4'-二甲基-2,2'-联吡啶（4,4'-（合成并表征CH ₃）₂ -bpy））。在单电子中氧化的[TpmRu ^II（L）（μ-CN）Fe ^III（dppe）Cp] [PF6] ₃在双核系统中，氰化物桥促进电子从Ru ^II离子转移到Fe ^III离子。随着L的取代从1,10-菲咯啉变为4,4'-二甲基-2,2'-联吡啶，它们的分子结构，循环伏安法，IR和UV呈现明显的变化趋势。此外，通过时间相关的密度泛函理论/密度泛函理论计算，可以合理地阐明MM'CT跃迁的分配以及具有不同L配体的不同混合配合物中的电子性质的差异。

更新日期：2018-04-30

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