American Chemical Society
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The Origin of Magnetic Anisotropy and Single-Molecule Magnet Behavior in Chromium(II)-Based Extended Metal Atom Chains

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posted on 2020-01-22, 13:40 authored by Andrea Cornia, Anne-Laure Barra, Vladimir Bulicanu, Rodolphe Clérac, Miguel Cortijo, Elizabeth A. Hillard, Rita Galavotti, Alessandro Lunghi, Alessio Nicolini, Mathieu Rouzières, Lorenzo Sorace, Federico Totti
Chromium­(II)-based extended metal atom chains have been the focus of considerable discussion regarding their symmetric versus unsymmetric structure and magnetism. We have now investigated four complexes of this class, namely, [Cr3(dpa)4X2] and [Cr5(tpda)4X2] with X = Cl and SCN [Hdpa = dipyridin-2-yl-amine; H2tpda = N2,N6-di­(pyridin-2-yl)­pyridine-2,6-diamine]. By dc/ac magnetic techniques and EPR spectroscopy, we found that all these complexes have easy-axis anisotropies of comparable magnitude in their S = 2 ground state (|D| = 1.5–1.8 cm–1) and behave as single-molecule magnets at low T. Ligand-field and DFT/CASSCF calculations were used to explain the similar magnetic properties of tri- versus pentachromium­(II) strings, in spite of their different geometrical preferences and electronic structure. For both X ligands, the ground structure is unsymmetric in the pentachromium­(II) species (i.e., with an alternation of long and short Cr–Cr distances) but is symmetric in their shorter congeners. Analysis of the electronic structure using quasi-restricted molecular orbitals (QROs) showed that the four unpaired electrons in Cr5 species are largely localized in four 3d-like QROs centered on the terminal, “isolated” Cr2+ ion. In Cr3 complexes, they occupy four nonbonding combinations of 3d-like orbitals centered only on the two terminal metals. In both cases, then, QRO eigenvalues closely mirror the 3d-level pattern of the terminal ions, whose coordination environment remains quite similar irrespective of chain length. We conclude that the extent of unpaired-electron delocalization has little impact on the magnetic anisotropy of these wire-like molecular species.