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Article

Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds

by 1,*, 1 and 2,3,*
1
Department of Chemistry, Bar-Ilan University, Ramat-Gan 5290002, Israel
2
CNR-SCITEC Istituto di Scienze e Tecnologie Chimiche “Giulio Natta”, Sezione di via Golgi, via Golgi 19, I-20133 Milano, Italy
3
Istituto Lombardo Accademia di Scienze e Lettere, via Brera 28, I-20121 Milano, Italy
*
Authors to whom correspondence should be addressed.
Academic Editor: Axel Klein
Molecules 2021, 26(11), 3069; https://doi.org/10.3390/molecules26113069
Received: 26 April 2021 / Revised: 14 May 2021 / Accepted: 19 May 2021 / Published: 21 May 2021
(This article belongs to the Special Issue New Directions in Metal–Metal Bond Chemistry)
Most of TM6-cluster compounds (TM = transition metal) are soluble in polar solvents, in which the cluster units commonly remain intact, preserving the same atomic arrangement as in solids. Consequently, the redox potential is often used to characterize structural and electronic features of respective solids. Although a high lability and variety of ligands allow for tuning of redox potential and of the related spectroscopic properties in wide ranges, the mechanism of this tuning is still unclear. Crystal chemistry approach was applied for the first time to clarify this mechanism. It was shown that there are two factors affecting redox potential of a given metal couple: Lever’s electrochemical parameters of the ligands and the effective ionic charge of TM, which in cluster compounds differs effectively from the formal value due to the bond strains around TM atoms. Calculations of the effective ionic charge of TMs were performed in the framework of bond valence model, which relates the valence of a bond to its length by simple Pauling relationship. It was also shown that due to the bond strains the charge depends mainly on the atomic size of the inner ligands. View Full-Text
Keywords: redox potential; Lever’s parameters; metal–metal bond; bond valence sum; steric effect; effective ionic charge redox potential; Lever’s parameters; metal–metal bond; bond valence sum; steric effect; effective ionic charge
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MDPI and ACS Style

Levi, E.; Aurbach, D.; Gatti, C. Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds. Molecules 2021, 26, 3069. https://doi.org/10.3390/molecules26113069

AMA Style

Levi E, Aurbach D, Gatti C. Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds. Molecules. 2021; 26(11):3069. https://doi.org/10.3390/molecules26113069

Chicago/Turabian Style

Levi, Elena, Doron Aurbach, and Carlo Gatti. 2021. "Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds" Molecules 26, no. 11: 3069. https://doi.org/10.3390/molecules26113069

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