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A T-shaped cyanidometal-bridged tetranuclear one-electron oxidized complex [{CpFeII(dppe)(CN)}3RuIII(DMPZ)2Cl][PF6]2 (1+, Cp = cyclopentadienyl; dppe = 1,2-bis(diphenylphosphino)ethane; DMPZ = 2,6-dimethylpyrazine), which can be considered as a composition of cis- and trans-configuration trinuclear subunits, was synthesized and well characterized. The FTIR and UV-vis-NIR spectra of products of 1+ with different valence states were investigated by spectroelectrochemical measurements on an OTLLE cell in dichloromethane. (TD)DFT calculations were performed to fully understand the metal-to-metal charge transfer (MMCT) transition and delocalization properties of the T-shaped cyanidometal-bridged tetranuclear complexes. Spectral analyses revealed a superior electronic delocalization between the terminal Fe centers positioned in the trans-configuration compared to those in the cis-configuration. Most importantly, this work shows the presence of the oxidation-driven intramolecular charge transfer from the terminal Fe center to the central Ru center during the change from the two-electron oxidized state (12+) to the three-electron oxidized state (13+), as confirmed by electrochemistry, FTIR and UV-vis-NIR spectroscopy, and also strongly supported by theoretical calculations.
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NEW JOURNAL OF CHEMISTRY
ISSN: 1144-0546
Year: 2025
Issue: 16
Volume: 49
Page: 6595-6602
2 . 7 0 0
JCR@2023
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ESI Highly Cited Papers on the List: 0 Unfold All
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30 Days PV: 1
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