Understanding the Electronic Structure of Magnetic Trinuclear Complexes Based on the Tris-Dioxolene Triphenylene Non-Innocent Bridging Ligand, a Theoretical Study - Archive ouverte HAL Access content directly
Journal Articles Chemistry - A European Journal Year : 2024

Understanding the Electronic Structure of Magnetic Trinuclear Complexes Based on the Tris-Dioxolene Triphenylene Non-Innocent Bridging Ligand, a Theoretical Study

Abstract

A complete theoretical analysis using first the simple Hückel model followed by more sophisticated multi-reference calculations on a trinuclear Ni(II) complex (Tp#Ni3HHTP), bearing the non-innocent bridging ligand HHTP3−, is carried out. The three semiquinone moieties of HHTP3− couple antiferromagnetically and lead to a single unpaired electron localized on one of the moieties. The calculated exchange coupling integrals together with the zero-field parameters allow, when varied within a certain range, reproducing the experimental data. These results are generalized for two similar other trinuclear complexes containing Ni(II) and Cu(II). The electronic structure of HHTP3− turns out to be independent of both the chemical nature and the geometry of the metal ions. We also establish a direct correlation between the geometrical and the electronic structures of the non-innocent ligand that is consistent with the results of calculations. It allows experimentalists to get insight into the magnetic behavior of this type of complexes by an analysis of their X-ray structure.

Dates and versions

hal-04431751 , version 1 (01-02-2024)

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Attribution - NonCommercial - NoDerivatives

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Nicolas Suaud, Aristide Colin, Mohammed-Amine Bouammali, Talal Mallah, Nathalie Guihéry. Understanding the Electronic Structure of Magnetic Trinuclear Complexes Based on the Tris-Dioxolene Triphenylene Non-Innocent Bridging Ligand, a Theoretical Study. Chemistry - A European Journal, 2024, 30, pp.e202302256. ⟨10.1002/chem.202302256⟩. ⟨hal-04431751⟩
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