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author:

Wang, Hao (Wang, Hao.) [1] | Liu, Xiao-Lin (Liu, Xiao-Lin.) [2] | Liu, Han (Liu, Han.) [3] | Wu, Xin-Tao (Wu, Xin-Tao.) [4] | Sheng, Tian-Lu (Sheng, Tian-Lu.) [5]

Indexed by:

EI

Abstract:

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. © 2025 The Royal Society of Chemistry.

Keyword:

Atomic emission spectroscopy Fourier transform infrared spectroscopy Near infrared spectroscopy Oxidation Spectroelectrochemistry

Community:

  • [ 1 ] [Wang, Hao]College of Chemistry, Fuzhou University, Fuzhou; 350108, China
  • [ 2 ] [Wang, Hao]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fujian, Fuzhou; 350002, China
  • [ 3 ] [Wang, Hao]Fujian College, University of Chinese Academy of Sciences, Fujian, Fuzhou; 350002, China
  • [ 4 ] [Liu, Xiao-Lin]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fujian, Fuzhou; 350002, China
  • [ 5 ] [Liu, Han]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fujian, Fuzhou; 350002, China
  • [ 6 ] [Wu, Xin-Tao]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fujian, Fuzhou; 350002, China
  • [ 7 ] [Sheng, Tian-Lu]College of Chemistry, Fuzhou University, Fuzhou; 350108, China
  • [ 8 ] [Sheng, Tian-Lu]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fujian, Fuzhou; 350002, China
  • [ 9 ] [Sheng, Tian-Lu]Fujian College, University of Chinese Academy of Sciences, Fujian, Fuzhou; 350002, China

Reprint 's Address:

  • [sheng, tian-lu]state key laboratory of structural chemistry, fujian institute of research on the structure of matter, chinese academy of science, fujian, fuzhou; 350002, china;;[sheng, tian-lu]college of chemistry, fuzhou university, fuzhou; 350108, china;;[sheng, tian-lu]fujian college, university of chinese academy of sciences, fujian, fuzhou; 350002, china

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Source :

New Journal of Chemistry

ISSN: 1144-0546

Year: 2025

Issue: 16

Volume: 49

Page: 6595-6602

2 . 7 0 0

JCR@2023

CAS Journal Grade:4

Cited Count:

WoS CC Cited Count:

SCOPUS Cited Count:

ESI Highly Cited Papers on the List: 0 Unfold All

WanFang Cited Count:

Chinese Cited Count:

30 Days PV: 1

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