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Issue 1, 2013
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Synthetic, structural, spectroscopic and theoretical study of a Mn(III)–Cu(II) dimer containing a Jahn–Teller compressed Mn ion

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Abstract

The heterobimetallic complex [Cu(II)Mn(III)(L)2(py)4](ClO4)·EtOH (1) built using the pro-ligand 2,2′-biphenol (LH2), contains a rare example of a Jahn–Teller compressed Mn(III) centre. Dc magnetic susceptibility measurements on 1 reveal a strong antiferromagnetic exchange between the Cu(II) and Mn(III) ions mediated through the phenolate O-atoms (J = −33.4 cm−1), with magnetisation measurements at low temperatures and high fields suggesting significant anisotropy. Simulations of high-field and high frequency powder EPR data suggest a single-ion anisotropy DMn(III) = +4.45 cm−1. DFT calculations also yield an antiferromagnetic exchange for 1, though the magnitude is overestimated (JDFT = −71 cm−1). Calculations reveal that the antiferromagnetic interaction essentially stems from the Mn(dx2y2)–Cu(dx2y2) interaction. The computed single-ion anisotropy and cluster anisotropy also correlates well with experiment. A larger cluster anisotropy for the S = 3/2 state compared to the single-ion anisotropy of Mn(III) is rationalised on the basis of orbital mixing and various contributions that arise due to the spin–orbit interaction.

Graphical abstract: Synthetic, structural, spectroscopic and theoretical study of a Mn(iii)–Cu(ii) dimer containing a Jahn–Teller compressed Mn ion

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Publication details

The article was received on 30 Aug 2012, accepted on 08 Oct 2012 and first published on 09 Oct 2012


Article type: Paper
DOI: 10.1039/C2DT31995K
Citation: Dalton Trans., 2013,42, 207-216
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    Synthetic, structural, spectroscopic and theoretical study of a Mn(III)–Cu(II) dimer containing a Jahn–Teller compressed Mn ion

    N. Berg, T. N. Hooper, J. Liu, C. C. Beedle, S. K. Singh, G. Rajaraman, S. Piligkos, S. Hill, E. K. Brechin and L. F. Jones, Dalton Trans., 2013, 42, 207
    DOI: 10.1039/C2DT31995K

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