Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds
Most of TM<sub>6</sub>-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 electroni...
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| Format: | Article |
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MDPI AG
2021-05-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/11/3069 |
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| author | Elena Levi Doron Aurbach Carlo Gatti |
| author_facet | Elena Levi Doron Aurbach Carlo Gatti |
| author_sort | Elena Levi |
| collection | DOAJ |
| description | Most of TM<sub>6</sub>-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. |
| first_indexed | 2024-03-10T11:11:07Z |
| format | Article |
| id | doaj.art-3d8fc0ee8c3d4a72bc8a043fabf2793c |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T11:11:07Z |
| publishDate | 2021-05-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-3d8fc0ee8c3d4a72bc8a043fabf2793c2023-11-21T20:46:37ZengMDPI AGMolecules1420-30492021-05-012611306910.3390/molecules26113069Redox Potential and Crystal Chemistry of Hexanuclear Cluster CompoundsElena Levi0Doron Aurbach1Carlo Gatti2Department of Chemistry, Bar-Ilan University, Ramat-Gan 5290002, IsraelDepartment of Chemistry, Bar-Ilan University, Ramat-Gan 5290002, IsraelCNR-SCITEC Istituto di Scienze e Tecnologie Chimiche “Giulio Natta”, Sezione di via Golgi, via Golgi 19, I-20133 Milano, ItalyMost of TM<sub>6</sub>-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.https://www.mdpi.com/1420-3049/26/11/3069redox potentialLever’s parametersmetal–metal bondbond valence sumsteric effecteffective ionic charge |
| spellingShingle | Elena Levi Doron Aurbach Carlo Gatti Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds Molecules redox potential Lever’s parameters metal–metal bond bond valence sum steric effect effective ionic charge |
| title | Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds |
| title_full | Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds |
| title_fullStr | Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds |
| title_full_unstemmed | Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds |
| title_short | Redox Potential and Crystal Chemistry of Hexanuclear Cluster Compounds |
| title_sort | redox potential and crystal chemistry of hexanuclear cluster compounds |
| topic | redox potential Lever’s parameters metal–metal bond bond valence sum steric effect effective ionic charge |
| url | https://www.mdpi.com/1420-3049/26/11/3069 |
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