Isomeric triarylamine-ferrocene mixed-valence systems: Syntheses, structural-(spectro)electrochemical analysis, and theoretical calculations

作者：Ou, Ya-Ping; Zhang, Qian; Yang, Xiaofei; Cao, Na; Jiang, Penghui; Liu, Sheng Hua^*

来源：Inorganica Chimica Acta, 2021, 528: 120603.

DOI：10.1016/j.ica.2021.120603

• Mixed-valence complexes
• Ferrocene
• Triarylamine
• Spectroelectrochemistry
• Theoretical calculations

Six novel triarylamine (TAA)-ferrocenyl conjugates (1-6) were prepared and characterized using molecular spectroscopic and crystallographic methods. Different species with a corresponding valences of 1n+ -6n+ (n = 0, 1) were investigated using cyclic voltammetry, UV-Vis-NIR spectroelectrochemistry, and quantum-chemical calculations. Electrochemical analysis of two groups of isomeric complexes (1-2) and complexes (3-6) revealed that the effective distance between redox-active ferrocenyl and TAA remarkably influenced the redox potential difference (Delta E). NIR peaked at 1142 and 1153 nm from singly oxidized complexes 1+ and 3+, thereby indicating that 1+ and 3+ were stable in CH2Cl2 solution and featured obvious IVCT characters. These findings were proved as NAr3 -> Fc charge transfer by TDDFT predictions. Calculations of spin density distribution showed that the monocations 1+-6+ all exhibited remarkably identical charge distributions with dominant metal (Fc)-localized characteristics.

• 单位
  衡阳师范学院