Issue 18, 2022

Effect of potential difference between the central and terminal metals on the electron communication in an Fe–Ru–Fe cyanidometal-bridged mixed valence system

Abstract

A series of trimetallic cyanidometal-bridged compounds with the formula [CpMexFe–NC–Ru–CN–FeCpMex]n+, Nn+ (n = 2, 3 and 4; N = 1, x = 0; N = 2, x = 1; N = 3, x = 3; N = 4, x = 4; N = 5, x = 5), were synthesized and fully characterized. The effect of the potential difference between the central and terminal metals on the electron communication in these trinuclear mixed valence systems was investigated. N3+ and N4+ are the one- and two-electron oxidation products of N2+. Electrochemical measurements show the presence of electronic interactions between the two terminal Fe atoms. The electronic properties of N3+ and N4+ were studied and compared using experimental spectroscopy and time-dependent density-functional calculations. As the number of methyl substituents on the cyclopentadiene ligand increases, the potential difference between the central and terminal redox centers increases and thus, the electron communication between the terminal Fe redox centers or between the neighboring Fe and Ru redox centers becomes weaker. All the mixed valence compounds show localized character.

Graphical abstract: Effect of potential difference between the central and terminal metals on the electron communication in an Fe–Ru–Fe cyanidometal-bridged mixed valence system

Supplementary files

Article information

Article type
Research Article
Submitted
27 Apr 2022
Accepted
08 Jul 2022
First published
13 Jul 2022

Inorg. Chem. Front., 2022,9, 4732-4740

Effect of potential difference between the central and terminal metals on the electron communication in an Fe–Ru–Fe cyanidometal-bridged mixed valence system

Y. Yang, X. Zhu, Y. Wang, X. Wu and T. Sheng, Inorg. Chem. Front., 2022, 9, 4732 DOI: 10.1039/D2QI00909A

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