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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Crown-6 rotator in spin-ladder compound of m-aminoanilinium([18]crown-6) [Ni(dmit)_2]~-
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Crown-6 rotator in spin-ladder compound of m-aminoanilinium([18]crown-6) [Ni(dmit)_2]~-

机译：间氨基苯胺（[18] cro-6）[Ni（dmit）_2]〜-的旋转梯状化合物中的Crown-6转子

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摘要

Supramolecular cations of HOPD~+([18]crown-6) and HMPD ~+([18]crown-6) were introduced into [Ni(dmit)_2] ~- salts (HOPD~+: o-aminoanilinium, HMPD~+: m-aminoanilinium, and dmit~(2-): 2-thioxo-1,3-dithiole-4,5-dithiolate). Alternate layers of cations and anions were observed in the two new salts of (HOPD~+)([18]crown-6)[Ni(dmit)_2]~- (1) and (HMPD~+)([18]crown-6)[Ni(dmit)_2]~- (2). From X-ray crystal structural analyses, solid state ~1H nuclear magnetic resonance (NMR) spectra, and dielectric constants, the thermal rotations of [18]crown-6 in both of the (HOPD~+)([18]crown-6) and (HMPD ~+)([18]crown-6) supramolecules occurred at temperatures above ～200 K based on the orientational disorder in the crystal structures. The two-fold flip-flop motions of HOPD~+ and HMPD~+ cations in salts 1 and 2 were suppressed, due to the relatively large potential energy barriers. The [Ni(dmit)_2]~- anion formed π-dimer arrangements in both salts, with a layer structure by lateral sulfur-sulfur interatomic contacts. Although the simple dimer model reproduced the magnetic properties of salt 1, the ladder arrangement of the π-dimer in salt 2 yielded the magnetic behavior of a spin-ladder with a spin-gap of 92.5 K. The temperature dependent magnetic susceptibility of salt 2 was well reproduced by the magnetic anisotropy of J_1/J_2≈ 8 between the ladder-leg (J_1: intra-dimer interaction) and ladder-rung (J _2: inter-dimer interaction). The [18]crown-6 supramolecular rotator of (HMPD~+)([18]crown-6) was coexistent with the spin-ladder chain of [Ni(dmit)_2]~- anions in salt 2.
机译：将HOPD〜+（[[18] crown-6）和HMPD〜+（[18] crown-6）的超分子阳离子引入[Ni（dmit）_2]〜-盐（HOPD〜+：邻氨基苯胺，HMPD〜 +：间氨基苯胺，和dmit（2-）：2-硫代-1，3-二硫代-4，5-二硫代）。在（HOPD〜+）（[18] crown-6）[Ni（dmit）_2]〜-（1）和（HMPD〜+）（[18] crown的两种新盐中观察到交替的阳离子和阴离子层-6）[Ni（dmit）_2]〜-（2）。通过X射线晶体结构分析，固态〜1H核磁共振（NMR）光谱和介电常数，[18] crown-6在（HOPD〜+）（[18] crown-6）中的热旋转）和（HMPD〜+）（[18] cro-6）超分子基于晶体结构中的取向紊乱而出现在〜200 K以上的温度下。盐1和2中HOPD〜+和HMPD〜+阳离子的两倍触发器运动由于相对较大的势能垒而受到抑制。 [Ni（dmit）_2]-阴离子在两种盐中均形成π-二聚体排列，并通过侧向硫-硫原子间接触形成层状结构。尽管简单的二聚体模型再现了盐1的磁性，但盐2中π二聚体的梯形排列却产生了自旋间隙为92.5 K的自旋阶梯的磁性能。盐2随温度变化的磁化率梯形腿（J_1：二聚体之间的相互作用）和梯形梯级（J_2：二聚体之间的相互作用）之间的J_1 /J_2≈8的磁各向异性很好地再现了这种现象。 （HMPD〜+）（[18] crown-6）的[18] crown-6超分子旋转子与盐2中的[Ni（dmit）_2]〜-阴离子的自旋梯形链共存。

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