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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

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http://xlink.rsc.org/?DOI=D0DT02731F
Original languageEnglish
JournalDalton Transactions
Early online date14 Oct 2020
DOIs
Publication statusE-pub ahead of print - 14 Oct 2020

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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