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Magneto-structural studies of an unusual [MnIIIMnIIGdIII(OR)4]4- partial cubane from 2,2'-bis-p-tBu-calix[4]arene.

  • Author(s): Coletta, Marco;
  • Sanz, Sergio;
  • Cutler, Daniel J;
  • Teat, Simon J;
  • Gagnon, Kevin J;
  • Singh, Mukesh K;
  • Brechin, Euan K;
  • Dalgarno, Scott J
  • et al.
Abstract

Reaction of 2,2'-bis-p-tBu-calix[4]arene (H8L) with MnCl2·4H2O, GdCl3·6H2O and 2,6-pyridinedimethanol (H2pdm) affords [MnIIIMnIIGdIII(H3L)(pdmH)(pdm)(MeOH)2(dmf)]·3MeCN·dmf (3·3MeCN·dmf) upon vapour diffusion of MeCN into the basic dmf/MeOH mother liquor. 3 crystallises in the tetragonal space group P41212 with the asymmetric unit comprising the entire cluster. The highly unusual core contains a triangular arrangement of MnIIIMnIIGdIII ions housed within a [MnIIIMnIIGdIII(OR)4]4- partial cubane. Magnetic susceptibility and magnetisation data reveal best fit parameters JMn(II)-Mn(III) = +0.415 cm-1, JMn(III)-Gd(III) = +0.221 cm-1, JMn(II)-Gd(III) = -0.258 cm-1 and DMn(III) = -4.139 cm-1. Theoretically derived magnetic exchange interactions, anisotropy parameters, and magneto-structural correlations for 3 are in excellent agreement with the experimental data.

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