Syntheses, crystal structures and MMCT properties of diruthenium-based cyanido-bridged RuV/VI2-NC-RuII complexes

Ting-Ya Li; Shao-Dong Su; Yong He; Xin-Tao Wu; Tian-Lu Sheng

doi:10.1039/d3dt01861j

Syntheses, crystal structures and MMCT properties of diruthenium-based cyanido-bridged RuV/VI2-NC-Ru^II complexes

Dalton Trans. 2024 Mar 12;53(11):5010-5019. doi: 10.1039/d3dt01861j.

Authors

Ting-Ya Li^{1

2}, Shao-Dong Su¹, Yong He^{1

2}, Xin-Tao Wu¹, Tian-Lu Sheng¹

Affiliations

¹ State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China. tsheng@fjirsm.ac.cn.
² University of the Chinese Academy of Sciences, Beijing 100049, China.

PMID: 38226679
DOI: 10.1039/d3dt01861j

Abstract

The goal of this study was to investigate how the electron-donating capability around the lower valent metal ion and the electron-accepting capability of the higher valent metal ion influence metal to metal charge transfer (MMCT) properties in mixed-valence complexes. A series of trinuclear ruthenium complexes represented as [Ru₂(ap-4-Me)₃(CH₃COO)NCRuCpMe_x(dppe)][PF₆] (CpMe_x = polymethylcyclopentadienyl, x = 0, 1, and 5; and dppe = 1, 2-bis(diphenylphosphino)ethane, ap-4-Me = 2-anilino-4-methylpyridine) and their one-electron oxidized products were synthesized and fully characterized. The UV-vis-NIR spectra confirmed that as the electron donor character of the CpMe_x(dppe)RuCN fragment enhanced or the electron-accepting capability of the higher valent diruthenium cluster increased, the Ru^II → RuV2 or RuVI2 Ru₂ MMCT bands shifted to lower energies, which was supported by TDDFT calculations.