Spin transitions in ferric catecholate complexes mediated by outer-sphere counteranions

A family of ionic ferric catecholate complexes 1-4 bearing a disubstituted 3,6-di- tert -butyl-catecholate ligand (3,6-DBCatH 2 ) and tetradentate tris(2-pyridylmethyl)amine (TPA) was prepared and its spin transitions were investigated. Variation of the outer-sphere counteranions (PF 6 , BPh 4 , ClO...

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Published in:Dalton transactions : an international journal of inorganic chemistry 2022-07, Vol.51 (29), p.199-1919
Main Authors: Chegerev, Maxim, Demidov, Oleg, Vasilyev, Pavel, Efimov, Nikolay, Kubrin, Stanislav, Starikov, Andrey, Vlasenko, Valery, Piskunov, Alexander, Shapovalova, Svetlana, Guda, Alexander, Rusalev, Yury, Soldatov, Alexander
Format: Article
Language:English
Subjects:
Crossovers
Crystal structure
Magnetic permeability
Magnetic properties
Single crystals
Spin transition
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Summary:A family of ionic ferric catecholate complexes 1-4 bearing a disubstituted 3,6-di- tert -butyl-catecholate ligand (3,6-DBCatH 2 ) and tetradentate tris(2-pyridylmethyl)amine (TPA) was prepared and its spin transitions were investigated. Variation of the outer-sphere counteranions (PF 6 , BPh 4 , ClO 4 , BF 4 ) is accompanied by changes in the magnetic behavior of the compounds under consideration. The crystal structures of complexes 1 , 3 and 4 were determined by single crystal X-ray diffraction analysis at 100 K and 293 K. The complexes were characterized by the occurrence of a thermally induced spin-crossover process in the solid state with different degrees of completeness, which was confirmed by the comprehensive spectroscopic investigation (EPR, magnetic susceptibility, Mössbauer, and XAS) of the isolated compounds. Complex 4 containing BF 4 anions was found to demonstrate valence tautomeric transition along with spin-crossover. This finding makes compound 4 the first salt-like mononuclear ferric catecholate complex exhibiting valence tautomerism. A family of ferric catecholate complexes exhibiting unusual magnetic properties is described.
ISSN:1477-9226
1477-9234
DOI:10.1039/d2dt01207c