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Issue 1, 2010
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A MnIII triplesalen-based 1D pearl necklace: exchange interactions and zero-field splittings in a C3-symmetric MnIII6 complex

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Abstract

The reaction of the tert-butyl-substituted triplesalen ligand H6talent-Bu2 with 2.8 equivalents of Mn(OAc)2·4H2O in MeOH in the presence of NaBPh4 results in the formation of the one-dimensional (1D) coordination polymer {[{(talent-Bu2)Mn3(MeOH)}22-OAc)3](μ2-OAc)}n(BPh4)2n ({[MnIII6](OAc)}n(BPh4)2n) which has been characterized by FTIR, elemental analysis, ESI-MS, single-crystal X-ray diffraction and magnetic measurements. The triplesalen ligand (talent-Bu2)6 provides three salen-like coordination compartments bridged in a meta-phenylene arrangement by a phloroglucinol backbone resulting in the trinuclear MnIII base unit {(talent-Bu2)Mn3}3+. Two of these base units are bridged by three inner acetate ligands giving rise to the hexanuclear complex [{(talent-Bu2)Mn3(MeOH)}22-OAc)3]3+ ([MnIII6]3+). These complexes are bridged by a single external acetate to form a 1D chain as pearls in a pearl necklace. Variable temperature-variable field and μeffvs. T magnetic data have been analyzed in detail by full-matrix diagonalization of the appropriate spin-Hamiltonian consisting of isotropic exchange, zero-field splitting, and Zeeman interaction taking into account the relative orientation of the D-tensors. Satisfactory reproduction of the experimental data have been obtained for parameters sets J1 = −(0.60 ± 0.15) cm−1, J2 = −(1.05 ± 0.15) cm−1, and DMn = −(3.0 ± 0.7) cm−1 with J1 describing the exchange through the phloroglucinol backbone and J2 describing the exchange through the inner acetates. The non-necessity to incorporate the bridging outer acetates correlates with the longer Mn–O bonds. The experimental data can neither be analyzed without incorporating zero-field splitting nor by the application of a single effective spin ground state.

Graphical abstract: A MnIII triplesalen-based 1D pearl necklace: exchange interactions and zero-field splittings in a C3-symmetric MnIII6 complex

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Publication details

The article was received on 26 Jun 2009, accepted on 04 Sep 2009 and first published on 07 Oct 2009


Article type: Paper
DOI: 10.1039/B912593K
Citation: Dalton Trans., 2010,39, 192-199

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    A MnIII triplesalen-based 1D pearl necklace: exchange interactions and zero-field splittings in a C3-symmetric MnIII6 complex

    T. Glaser, M. Heidemeier, H. Theil, A. Stammler, H. Bögge and J. Schnack, Dalton Trans., 2010, 39, 192
    DOI: 10.1039/B912593K

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