Magneto-structural studies of an unusual [MnIIIMnIIGdIII(OR)4]4- partial cubane from 2,2'-bis-p-tBu-calix[4]arene.
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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DOI：
10.1039/d0dt02731f
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发表时间：
2020-10
影响因子：
4
通讯作者：
Marco Coletta;S. Sanz;Daniel J Cutler;S. Teat;Kevin J. Gagnon;Mukesh K Singh;E. Brechin;S. Dalgarno
中科院分区：
文献类型：
--
作者：
Marco Coletta;S. Sanz;Daniel J Cutler;S. Teat;Kevin J. Gagnon;Mukesh K Singh;E. Brechin;S. Dalgarno
2,2'-双-p-tBu-杯[4]芳烃 (H8L) 与 MnCl2·4H2O、GdCl3·6H2O 和 2,6-吡啶二甲醇 (H2pdm) 反应得到 [MnIIIMnIIGdIII(H3L)(pdmH)(pdm)(MeOH)2(dmf)]·3MeCN·dmf (3·3MeCN·dmf) 将 MeCN 蒸气扩散到碱性 dmf/MeOH 母液中。 3在四方空间群P41212中结晶，不对称单元构成整个簇。这个非常不寻常的核心包含三角形排列的 MnIIIMnIIGdIII 离子，位于 [MnIIIMnIIGdIII(OR)4]4- 部分立方烷内。磁化率和磁化强度数据揭示了最佳拟合参数 JMn(II)-Mn(III) = +0.415 cm-1、JMn(III)-Gd(III) = +0.221 cm-1、JMn(II)-Gd(III) = -0.258 cm-1 和 DMn(III) = -4.139 cm-1。理论上得出的 3 的磁交换相互作用、各向异性参数和磁结构相关性与实验数据非常一致。
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.