Optical detection of spin polarization in single-molecule magnets Mn12O12(O2CR)16(H2O)4

Eric J. L. McInnes, Elna Pidcock, Vasily S. Oganesyan, Myles R. Cheesman, Annie K. Powell, Andrew J. Thomson

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A magneto-optical study has been undertaken of the mixed-valence single-molecule magnet [(Mn4Mn8O12L16)-Mn-IV-O-III] in which the ligands, L, are acetate (Mn12Ac) or the long-chain carboxylic acid, C14H29COOH (Mn12C15), that confers better solubility in organic solvents. Thin polymer films of these compounds in poly(methyl methacrylate) (PMM) have been cast by solvent evaporation to provide samples suitable for variable-temperature and field magnetic circular dichroism (MCD) studies. The absorption spectra in isotropic light are featureless, whereas the low-temperature MCD spectra contain resolved peaks, both positive and negative. MCD magnetization curves measured at temperatures above 4.2 K have established a ground-state spin of S = 10 and an axial zero-field parameter, D, of -0.61 K, similar to that determined for single crystals of Mn12Ac. By studying at a variety of optical wavelengths, the polarization ratios of the optical transitions relative to the unique axis of the zero-field distortion have been determined. The MCD magnetization curves measured at 4.2 K between 0 and 5 T for the case of Mln(12)C(15) in the PMM film can be fitted only on the assumption of nonrandom distribution of molecular z-axes arising from stresses in the polymer film during the process of casting. MCD-detected hysteresis curves measured in both frozen solution and PMM films, below the blocking temperature of similar to3 K, show a high retention of spin polarization after reduction to zero of a polarizing magnetic field. This generates intense zero-field circular dichroism (CD) with maximum intensity for xy-polarized optical transitions whose sign depends on the direction of the original polarizing field. The optical polarization and the selection rules for MCD select a subset of molecular orientations with respect to the direction of field. Thus, the magnetically induced CD provides a highly sensitive and rapid optical method of reading the spin polarization of molecular magnets.
Original languageEnglish
Pages (from-to)9219-9228
Number of pages10
JournalJournal of the American Chemical Society
Issue number31
Publication statusPublished - 2002

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