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Issue 26, 2006
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Enhancing single molecule magnet parameters. Synthesis, crystal structures and magnetic properties of mixed-valent Mn4 SMMs

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Abstract

A novel synthetic route is reported for the synthesis of three dicubane complexes [MnII2MnIII2(bdea)2(bdeaH)2(O2CCMe3)4] (1), [MnII2MnIII2(bdea)2(bdeaH)2(O2CPh)4] (2), and [MnII2MnIII2(teaH)2(teaH2)2(O2CPh)2](O2CPh)2·0.7MeCN·0.3EtOH (3), obtained from the reaction of N-butyldiethanolamine (bdeaH2, for 1 and 2) or triethanolamine (teaH3, for 3) with Mn(OAc)2·4H2O as manganese source and [M3O(O2CR)6](O2CR) (R = CMe3 for 1, and Ph for 2 and 3 and M: Fe or Mn) compounds as carboxylate source. Complex 1 crystallises in the monoclinic space group P21/c (a = 13.2125(7) Å, b = 10.9602(6) Å, c = 22.2329(11) Å, β = 95.053(1)°, V = 3235.9(3) Å3, with Z = 2). Complex 2 crystallises in the monoclinic space group P21/n (a = 16.6894(14) Å, b = 8.7360(7) Å, c = 21.3378(18) Å, β = 92.949(2)°, V = 3106.9(4) Å3, with Z = 2). Complex 3 crystallises in the monoclinic space group C2/c (a = 30.242(3) Å, b = 8.6710(6) Å, c = 26.618(3) Å, β = 119.915(9)°, V = 6050.0(10) Å3, with Z = 4). The X-ray crystallographic structure analyses revealed that 1–3 are essentially isostructural, each consisting of a planar mixed-valent “butterfly” core lying about an inversion centre and comprising two outer “wingtip” heptacoordinate MnII ions and two inner hexacoordinate MnIII. Magnetic properties have been studied for all three complexes using combined ac and dc measurements, revealing single-molecule magnet (SMM) behaviour for 1–3, with an S = 9 spin ground state. A detailed analysis of the slow relaxation of the magnetisation has been performed to characterise their SMM behaviour.

Graphical abstract: Enhancing single molecule magnet parameters. Synthesis, crystal structures and magnetic properties of mixed-valent Mn4 SMMs

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Supplementary files

Article information


Submitted
30 Mar 2006
Accepted
18 Apr 2006
First published
12 May 2006

J. Mater. Chem., 2006,16, 2579-2586
Article type
Paper

Enhancing single molecule magnet parameters. Synthesis, crystal structures and magnetic properties of mixed-valent Mn4 SMMs

A. M. Ako, V. Mereacre, I. J. Hewitt, R. Clérac, L. Lecren, C. E. Anson and A. K. Powell, J. Mater. Chem., 2006, 16, 2579
DOI: 10.1039/B604611H

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