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Ovcharenko VI, Gorelik EV, Fokin SV, et al. Ligand effects on the ferro- to antiferromagnetic exchange ratio in bis(o-semiquinonato)copper(II). J Am Chem Soc. 2007;129(34):10512-21doi: 10.1021/ja072463b.
Ovcharenko, V. I., Gorelik, E. V., Fokin, S. V., Romanenko, G. V., Ikorskii, V. N., Krashilina, A. V., Cherkasov, V. K., & Abakumov, G. A. (2007). Ligand effects on the ferro- to antiferromagnetic exchange ratio in bis(o-semiquinonato)copper(II). Journal of the American Chemical Society, 129(34), 10512-21. https://doi.org/10.1021/ja072463b
Ovcharenko, Victor I, et al. "Ligand effects on the ferro- to antiferromagnetic exchange ratio in bis(o-semiquinonato)copper(II)." Journal of the American Chemical Society vol. 129,34 (2007): 10512-21. doi: https://doi.org/10.1021/ja072463b
Ovcharenko VI, Gorelik EV, Fokin SV, Romanenko GV, Ikorskii VN, Krashilina AV, Cherkasov VK, Abakumov GA. Ligand effects on the ferro- to antiferromagnetic exchange ratio in bis(o-semiquinonato)copper(II). J Am Chem Soc. 2007 Aug 29;129(34):10512-21. doi: 10.1021/ja072463b. Epub 2007 Aug 03. PMID: 17676737.
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J Am Chem Soc. 2007 Aug 29;129(34):10512-21. doi: 10.1021/ja072463b. Epub 2007 Aug 03.

Ligand effects on the ferro- to antiferromagnetic exchange ratio in bis(o-semiquinonato)copper(II).

Journal of the American Chemical Society

Victor I Ovcharenko, Elena V Gorelik, Sergey V Fokin, Galina V Romanenko, Vladimir N Ikorskii, Anna V Krashilina, Vladimir K Cherkasov, Gleb A Abakumov

Affiliations

  1. International Tomography Center, Russian Academy of Sciences, 3A Institutskaya Street, 630090 Novosibirsk, Russian Federation. [email protected]

PMID: 17676737 DOI: 10.1021/ja072463b

Abstract

Heterospin complexes [Cu(SQ)2Py].C7H8, Cu(SQ)2DABCO, and [Cu(SQ)2NIT-mPy].C6H6, where Cu(SQ)2 is bis(3,6-di-tert-butyl-o-benzosemiquinonato)copper(II), DABCO is 1,4-diazabicyclo(2,2,2)octane, and NIT-mPy is the nitronyl nitroxide 2-(pyridin-3-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl, have been synthesized. The molecules of these complexes have a specific combination of the intramolecular ferro- and antiferromagnetic exchange interactions between the odd electrons of Cu(II) and SQ ligands, characterized by large exchange coupling parameters |J| approximately 100-300 cm(-1). X-ray and magnetochemical studies of a series of mixed-ligand compounds revealed that an extra ligand (Py, NIT-mPy, or DABCO) coordinated to the metal atom produces a dramatic effect on the magnetic properties of the complex, changing the multiplicity of the ground state. Quantum chemical analysis of magnetostructural correlations showed that the energy of the antiferromagnetic exchange interaction between the odd electrons of the SQ ligands in the Cu(SQ)2 bischelate is extremely sensitive to both the nature of the extra ligand and structural distortions of the coordination unit, arising from extra ligand coordination.

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