期刊
DALTON TRANSACTIONS
卷 40, 期 44, 页码 11968-11975出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c1dt11242b
关键词
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资金
- Ministerio de Ciencia e Innovacion of Spain [CTQ2009-07264/BQU]
- Comissio Interdepartamental de Recerca i Innovacio Tecnologica of la Generalitat de Catalunya (CIRIT) [2009-SGR1454]
- Ministerio de Ciencia e Innovacion [BES-2007-15668]
- Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy [DE-AC02-05CH11231]
Three dinuclear Mn(III) compounds with oxo and carboxylato bridges have been synthesized and characterized by X-ray diffraction: [{Mn(L)(NN)}(mu-2-ClC6H4COO)(2)(mu-O){Mn(L')(NN)}](n+) with NN = 2,2'-bipyridine (1 and 2) or 1,10-phenanthroline (3). The counteranion is either NO3-(1 and 3) or ClO4- (2) and the monodentate positions (L, L') could be occupied by molecules of water or the counteranion. For compound 1, L = H2O and L' = NO3-; compound 2 shows two different dinuclear units and L and L' could be H2O or ClO4-, and for compound 3 both monodentate positions are occupied by nitrate anions. The magnetic properties of the three compounds have been analyzed using the Hamiltonian H = -JS(1).S-2. Compound 1 exhibits a dominant ferromagnetic behavior, with J = 3.0 cm(-1), vertical bar D-Mn vertical bar = 1.79 cm(-1), vertical bar E-Mn vertical bar = 0.60 cm(-1) with intermolecular interactions zJ' = -0.18 cm(-1). Due to the anisotropy of the Mn(III) ions, the ground state S = 4 shows ZFS with vertical bar D-4 vertical bar = 0.58 cm(-1). Compounds 2 and 3 show antiferromagnetic couplings, with J = -10.9 and -0.3 cm(-1), respectively. The magnetic interaction in this kind of compound depends on several structural factors. In the present work, the distortion around manganese ions, the torsion angle between the phenyl ring and the carboxylate group and the relative disposition of the coordination octahedra have been analyzed.
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