Issue 24, 2023

Tuning the magnetic properties of dinuclear cobalt–tetraoxolene compounds: from valence tautomerism to ferromagnetic coupling

Abstract

The reaction of a non-innocent ligand 2,7-di-tert-butyl-pyrene-4,5,9,10-tetraone (pyreneQ–Q, Q = quinone), Co2(CO)8, and tris(2-pyridylmethyl)amine derivatives (Mentpa) gave rise to a series of dinuclear cobalt–tetraoxolene compounds formulated as {[Co(Mentpa)]2(pyreneSq–Sq)}[Co(CO)4]2·S (Sq = semiquinone; n = 0, S = 2C6H5CH3 for 3; n = 1 for 4; n = 2, S = 2CHCl3 for 5). Magnetic measurements and single-crystal X-ray diffraction studies revealed that compound 3 underwent incomplete valence tautomeric transition, while compounds 4 and 5 maintained in the steady electronic structure of {CoII-HS–pyreneSq–Sq–CoII-HS} in the whole temperature range. Remarkably, strong ferromagnetic interactions in both 4 and 5 were confirmed by experimental and theoretical studies. Theoretical calculations showed that the successive introduction of methyl groups enhanced the steric rigidity of tpa, and hence the {CoII-HS–pyreneSq–Sq–CoII-HS} state was stabilized sterically and electronically, which in turn altered the energetic order and gap among the different electronic states, which resulted in distinct magnetic properties.

Graphical abstract: Tuning the magnetic properties of dinuclear cobalt–tetraoxolene compounds: from valence tautomerism to ferromagnetic coupling

Supplementary files

Article information

Article type
Research Article
Submitted
25 Aug. 2023
Accepted
20 Okt. 2023
First published
24 Okt. 2023

Inorg. Chem. Front., 2023,10, 7251-7264

Tuning the magnetic properties of dinuclear cobalt–tetraoxolene compounds: from valence tautomerism to ferromagnetic coupling

Y. Zhao, J. Wang, X. Chen, M. Yu, A. A. Starikova and J. Tao, Inorg. Chem. Front., 2023, 10, 7251 DOI: 10.1039/D3QI01706K

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