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

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 rutheniu...

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Published inDalton transactions : an international journal of inorganic chemistry Vol. 53; no. 11; pp. 5010 - 5019
Main Authors Li, Ting-Ya, Su, Shao-Dong, He, Yong, Wu, Xin-Tao, Sheng, Tian-Lu
Format Journal Article
LanguageEnglish
Published England 12.03.2024
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Summary: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 [Ru (ap-4-Me) (CH COO)NCRuCpMe (dppe)][PF ] (CpMe = polymethylcyclopentadienyl, = 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 (dppe)RuCN fragment enhanced or the electron-accepting capability of the higher valent diruthenium cluster increased, the Ru → RuV2 or RuVI2 Ru MMCT bands shifted to lower energies, which was supported by TDDFT calculations.
ISSN:1477-9226
1477-9234
DOI:10.1039/D3DT01861J