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With complements of the ligands: an unusual S-shaped [Mn7]2 assembly from tethered calixarenes.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-07-08 , DOI: 10.1039/d0dt01766c
Marco Coletta 1 , Sergio Sanz 2 , Euan K Brechin 2 , Scott J Dalgarno 3
Affiliation  

The reaction between MnCl2·4H2O, 2,2′-bis-p-tBu-calix[4]arene (H8L1) and 2-(hydroxymethyl)pyridine (hmpH) in a basic dmf/MeOH solution results in the formation of the complex [MnIII10MnII4(L1)3(hmp)43-O)43-OH)2(MeOH)4(dmf)6](dmf)4 (6) upon vapour diffusion of petroleum ether into the mother liquor. The crystals are in the monoclinic space group C2/c, with the asymmetric unit (ASU) comprising one half of the molecule. The structure describes a large S-shaped cluster (∼40 Å top to tail) where the unusual syn and anti conformations of the calixarene ligands results in two binding pockets each containing a [MnIII5MnII2] moiety comprised of two perpendicular, vertex-sharing [Mn4] butterflies. One butterfly possesses a [MnIII4O4] core and the second a [MnIII2MnII2O3] unit with the MnII ions in the central body positions. Magnetic susceptibility and magnetisation measurements reveal weak exchange interactions between the metal centres.

中文翻译:

具有配体的互补物:由杯状芳烃连接而成的不寻常的S形[Mn7] 2组装体。

的MnCl之间的反应2 ·4H 2 O,2,2'-双p -卜杯[4]芳烃(H 8在碱性DMF L1)和2-(羟甲基)吡啶(哼)/ MeOH溶液的结果在配合物[Mn的形成III 10II 4(L1)3(HMP)4(μ 3 -O)4(μ 3 -OH)2(甲醇)4(DMF)6 ](DMF)46)石油醚蒸气扩散到母液中。晶体在单斜空间群C中2 / c,其中不对称单元(ASU)占分子的一半。该结构描述了一个大的S形簇(从上到尾约40Å),其中杯芳烃配体的异常顺式反式构象导致两个结合袋,每个结合袋包含[Mn III 5 Mn II 2 ]部分,由两个垂直的,顶点共享[Mn 4 ]蝴蝶。一个蝶形拥有[锰III 4 Ò 4 ]芯和第二A [的Mn III 2II 2 ö 3 ]单元与MN II离子在身体中央位置。磁化率和磁化强度测量表明,金属中心之间的交换作用较弱。
更新日期:2020-07-21
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