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一种混合层状化合物的合成、晶体与网络结构及磁性质:[K(18-冠醚)(2-丙醇)(2)][{Mn(乙酰丙酮二胺)}(2){Fe(氰化钾)}(6)](18-冠醚 = 18-冠-6-醚,乙酰丙酮二胺 = N,N'-亚乙基双(乙酰丙酮亚胺基))

Synthesis, Crystal and Network Structures, and Magnetic Properties of a Hybrid Layered Compound: [K(18-cr)(2-PrOH)(2)][{Mn(acacen)}(2){Fe(CN)(6)}] (18-cr = 18-Crown-6-ether, acacen = N,N'-Ethylenebis(acetylacetonylideneiminate)).

作者信息

Miyasaka Hitoshi, Okawa Hisashi, Miyazaki Akira, Enoki Toshiaki

机构信息

Department of Chemistry, Faculty of Science, Kyushu University, Hakozaki 6-10-1, Higashi-ku, Fukuoka 812-81, Japan, and Department of Chemistry, Tokyo Institute of Technology, Ookayama 2-12-1, Meguro-ku, Tokyo 152-8551, Japan.

出版信息

Inorg Chem. 1998 Sep 21;37(19):4878-4883. doi: 10.1021/ic980448p.

Abstract

A hybrid layered compound [{K(18-cr)(2-PrOH)(2)}{Mn(acacen)}(2){Fe(CN)(6)}] has been prepared by the reaction of [Mn(acacen)(Cl)] with K(18-cr)(H(2)O)(2)[Fe(CN)(6)].3H(2)O in an ethanol/2-propanol mixed solvent (18-cr = 18-crown-6-ether, acacen = N,N'-ethylenebis(acetylacetonylideneiminate)). It crystallizes in the monoclinic space group P2(1)/a with cell dimensions of a = 13.272(3) Å, b = 15.768 (2) Å, c = 14.771(2) Å, beta = 105.64(1) degrees, Z = 2. It assumes a hybrid layered structure of alternating arrays of two types of layers. One of the layers is formed by the anionic part {Mn(acacen)}(2){Fe(CN)(6)}()(n)()(-), where Fe(CN)(6)(-) coordinates through its four cyanide groups on a plane to the axial sites of four Mn(acacen) entities. The two-dimensional layer consists of the cyclic octamer -Mn-NC-Fe-CN- having the Fe ions at the corners and the Mn ions on the edges of a deformed square. Another layer is formed by the cationic part K(18-cr)(2-PrOH)(2) that has a hexagonal-bipyramidal geometry about the metal with two 2-PrOH molecules at the apexes of the nearly planar K(18-cr). The anionic and cationic layers are combined by the hydrogen bond between the cyanide groups (free from coordination) of the anionic layer and the 2-propanol groups of the cationic layer with bond distance of N.O = 2.861(5) Å. Magnetic studies (magnetic susceptibility vs T, field-cooled magnetization vs T, saturation magnetization vs H) indicate that the compound is a metamagnet with a Néel temperature T(N) = 5.0 K, showing the onset of ferromagnetic ordering within the anionic layer and an antiferromagnetic interlayer interaction. Magnetization as a function of the applied magnetic field indicates a spin-flipping from antiferromagnetic arrangement to ferromagnetic arrangement between the layers around 1200 Oe and exhibits hysteresis behavior.

摘要

通过在乙醇/2-丙醇混合溶剂中使[Mn(acacen)(Cl)]与[K(18-cr)(H₂O)₂]₃[Fe(CN)₆]·3H₂O反应,制备了一种杂化层状化合物[{K(18-cr)(2-PrOH)₂}{Mn(acacen)}₂{Fe(CN)₆}](18-cr = 18-冠-6-醚,acacen = N,N'-亚乙基双(乙酰丙酮亚胺))。它结晶于单斜空间群P2(1)/a,晶胞参数为a = 13.272(3) Å,b = 15.768(2) Å,c = 14.771(2) Å,β = 105.64(1)°,Z = 2。它呈现出由两种类型的层交替排列组成的杂化层状结构。其中一层由阴离子部分[{Mn(acacen)}₂{Fe(CN)₆}]ⁿ⁻形成,其中[Fe(CN)₆]³⁻通过其平面上的四个氰基与四个[Mn(acacen)]⁺实体的轴向位点配位。二维层由环状八聚体[-Mn-NC-Fe-CN-]₄组成,Fe离子位于变形正方形的角上,Mn离子位于边上。另一层由阳离子部分[K(18-cr)(2-PrOH)₂]⁺形成,其围绕金属具有六方双锥几何结构,在近乎平面的[K(18-cr)]⁺的顶点处有两个2-丙醇分子。阴离子层和阳离子层通过阴离子层中未参与配位的氰基与阳离子层中的2-丙醇基团之间的氢键结合,键长N···O = 2.861(5) Å。磁性研究(磁化率对T、场冷磁化强度对T、饱和磁化强度对H)表明该化合物是一种变磁体,奈尔温度T(N) = 5.0 K,表明在阴离子层内开始出现铁磁有序,且层间存在反铁磁相互作用。磁化强度作为外加磁场的函数表明,在1200 Oe左右,层间自旋从反铁磁排列翻转到铁磁排列,并表现出磁滞行为。

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