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Domingo A, Vérot M, Mota F, et al. Impact of short and long-range effects on the magnetic interactions in neutral organic radical-based materials. Phys Chem Chem Phys. 2013;15(18):6982-9doi: 10.1039/c3cp44647f.
Domingo, A., Vérot, M., Mota, F., de Graaf, C., Novoa, J. J., & Robert, V. (2013). Impact of short and long-range effects on the magnetic interactions in neutral organic radical-based materials. Physical chemistry chemical physics : PCCP, 15(18), 6982-9. https://doi.org/10.1039/c3cp44647f
Domingo, Alex, et al. "Impact of short and long-range effects on the magnetic interactions in neutral organic radical-based materials." Physical chemistry chemical physics : PCCP vol. 15,18 (2013): 6982-9. doi: https://doi.org/10.1039/c3cp44647f
Domingo A, Vérot M, Mota F, de Graaf C, Novoa JJ, Robert V. Impact of short and long-range effects on the magnetic interactions in neutral organic radical-based materials. Phys Chem Chem Phys. 2013 May 14;15(18):6982-9. doi: 10.1039/c3cp44647f. Epub 2013 Apr 04. PMID: 23552727.
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Phys Chem Chem Phys. 2013 May 14;15(18):6982-9. doi: 10.1039/c3cp44647f. Epub 2013 Apr 04.

Impact of short and long-range effects on the magnetic interactions in neutral organic radical-based materials.

Physical chemistry chemical physics : PCCP

Alex Domingo, Martin Vérot, Fernando Mota, Coen de Graaf, Juan J Novoa, Vincent Robert

Affiliations

  1. Laboratoire de Chimie Quantique, Institut de Chimie UMR 7177, Université de Strasbourg, 4 rue Blaise Pascal, 67081 Strasbourg, France. [email protected]

PMID: 23552727 DOI: 10.1039/c3cp44647f

Abstract

The mutual influence of electronic structure and environment of the constituent units of neutral organic radical-based materials (radical dimers) is analysed by means of wave function calculations (Difference Dedicated Configuration Interaction, DDCI). Focus is put on the magnetic property modulations of two classes of neutral organic materials by inspecting both short- and long-range effects. The exchange coupling constant J for the high-temperature phase of the 1,3,5-trithia-2,4,6-triazapentalenyl (TTTA) material is calculated to be J= -95 cm(-1) at the DDCI level. The environmental electronic polarization is taken into account self-consistently using the individual polarizabilities of the atoms in a finite block of the crystal lattice (Discrete Reaction Field, DRF) and accounts for less than 5% of the calculated J value in TTTA. Furthermore, taking advantage of the chemical flexibility of the verdazyl radical family, the contribution of strong electron-withdrawing groups is analysed by extracting the J, U, t and K parameters from pairs of substituted verdazyl-based radicals. Our ab initio calculations of verdazyl radical pairs suggest that the addition of NO2 groups cause (i) the variations of the ferromagnetic and antiferromagnetic contributions to cancel out, leaving an almost constant exchange coupling constant, ca. J≈ 20 cm(-1), and that (ii) enhanced conduction properties can be anticipated. In contrast to inorganic analogues, one may conclude that the magnetic behaviour of neutral organic radical-based materials is mostly governed by the supramolecular arrangement, whereas environmental effects have a lesser impact.

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