Electron-Transfer-Induced Structural Modification in a Thermochromic Hofmann Clathrate Derivative

This study explores a Hofmann-type clathrate, {Fe<sub>2</sub>(2,4-(OCH<sub>3</sub>)<sub>2</sub>-<i>p</i>bpy)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>[μ<sub>2</sub>-Pt(CN)<sub>4</sub>][μ<sub>3</sub>-Pt(CN)<sub>4</sub>]<sub>2</sub>·4H<sub>2</sub>O}, which exhibits a thermally activated electron transfer (ET) without spin crossover. Synthesized as microcrystalline powders and single crystals, this compound reveals significant structural changes upon variation of the temperature, including alterations in the iron coordination sphere due to the large movement of the bipyridinium ligand. These changes correlate with a thermochromic hysteretic transition from yellow to orange. Detailed characterizations using X-ray diffraction and IR spectroscopy indicate the involvement of nonbridging CN<sup>-</sup> moieties as electron donors and bipyridinium units as acceptors. This result deepens our understanding of ET in Hofmann-type clathrates.

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Publication Details

Journal
Inorganic Chemistry
Published
2024-11-28
DOI
https://doi.org/10.1021/acs.inorgchem.4c04155
Citations
5
Primary Topic
Magnetism in coordination complexes
Type
article
Field-Weighted Citation Impact
0.59

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article

Electron-Transfer-Induced Structural Modification in a Thermochromic Hofmann Clathrate Derivative

Saioa Cobo, Laure Vendier, Gábor Molnár, Zakaria Ziani et al.
5 citations
Inorganic Chemistry
Magnetism in coordination complexes
0.59
article

Electron-Transfer-Induced Structural Modification in a Thermochromic Hofmann Clathrate Derivative

Saioa Cobo, Laure Vendier, Gábor Molnár, Zakaria Ziani, Livia Getzner, Azzedine Bousseksou, Yasmine Remili
article en
5 citations

Abstract

This study explores a Hofmann-type clathrate, {Fe<sub>2</sub>(2,4-(OCH<sub>3</sub>)<sub>2</sub>-<i>p</i>bpy)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>[μ<sub>2</sub>-Pt(CN)<sub>4</sub>][μ<sub>3</sub>-Pt(CN)<sub>4</sub>]<sub>2</sub>·4H<sub>2</sub>O}, which exhibits a thermally activated electron transfer (ET) without spin crossover. Synthesized as microcrystalline powders and single crystals, this compound reveals significant structural changes upon variation of the temperature, including alterations in the iron coordination sphere due to the large movement of the bipyridinium ligand. These changes correlate with a thermochromic hysteretic transition from yellow to orange. Detailed characterizations using X-ray diffraction and IR spectroscopy indicate the involvement of nonbridging CN<sup>-</sup> moieties as electron donors and bipyridinium units as acceptors. This result deepens our understanding of ET in Hofmann-type clathrates.

Inorganic ChemistryVol. 63(50)
Centre National de la Recherche Scientifique (FR), Université Toulouse III - Paul Sabatier (FR), Université Fédérale de Toulouse Midi-Pyrénées (FR), Institut National Polytechnique de Toulouse (FR), Laboratoire de Chimie de Coordination (FR)
European Commission, Agence Nationale de la Recherche, Unitatea Executiva pentru Finantarea Invatamantului Superior, a Cercetarii, Dezvoltarii si Inovarii, Université Toulouse III - Paul Sabatier, H2020 European Research Council
Openalex Percentile: Top 39%
Magnetism in coordination complexes
0.59
DOIOpen Access PDFOpenAlex
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