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Computational study of the structure and magnetic properties of the weakly-coupled tetranuclear square-planar complex of Cu(II) with a tetraporphyrin sheet
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-0716-3385
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-1763-9383
2019 (English)In: Inorganica Chimica Acta, ISSN 0020-1693, E-ISSN 1873-3255, Vol. 485, p. 73-79Article in journal (Refereed) Published
Abstract [en]

Owing to the fact that weakly-coupled Cu(II) complexes are potentially applicable in the fields of spintronics and single-molecule magnets we have studied one particularly conspicuous case – a tetranuclear square-planar complex of Cu(II) ions with a π-extended tetraporphyrin ligand (Tetrahedron, 2008, 64, 11433), the structural criteria of which, with very long distances between the paramagnetic centers, can sensibly define the exchange coupling constants and magnetic behaviour. We use the “broken symmetry” density functional theory formalism for various spin states (open-shell singlet, triplet and quintet states). The calculated value of the magnetic exchange integral corresponds to a very weak antiferromagnetic coupling between the neighboring Cu(II) ions (Jcalc = –1.48 cm−1(calculated) Jexp = −1.16 cm−1 (experiment)). The opposite Cu(II) ions are coupled ferromagnetically with an extremely small exchange constant (jcalc = 0.09 cm−1 (calculated) that corresponds to the open-shell singlet ground state of the following spin configuration↑↓↑↓. The exchange mechanism between the [Cu(n) + 4N] localized singly-occupied “magnetic” orbitals of the dxy(Cu) + 4sp2(N) nature indicates a diffuse non-zero overlap between them on the Carbon atoms of the organic ligand. The numerical analysis of atomic spin densities and corresponding decomposition coefficients for the singly-occupied “magnetic” orbitals confirm the proposed exchange mechanism. This superexchange pathway is mediated by the in-plane sp2-hybrid orbitals of the Carbon atoms that couple four [Cu + 4N] fragments by the σ-bond system. For more detailed characterization of the target system a topological analysis of electron density distributions in the high-spin quintet states has been carried out using the Bader's method “quantum theory of atoms in molecules”.

Place, publisher, year, edition, pages
Elsevier S.A. , 2019. Vol. 485, p. 73-79
Keywords [en]
Antiferromagnetic coupling, Bader analysis, Cu(II) complexes, Magnetic exchange, Open-shell singlet, “broken symmetry” approximation
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-248246DOI: 10.1016/j.ica.2018.09.086ISI: 000448409900011Scopus ID: 2-s2.0-85054463547OAI: oai:DiVA.org:kth-248246DiVA, id: diva2:1304145
Note

QC 20190411

Available from: 2019-04-11 Created: 2019-04-11 Last updated: 2019-04-11Bibliographically approved

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Baryshnikov, Gleb V.Ågren, Hans
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