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首页> 外文期刊>Crystal growth & design >Hexanuclear 3d-4f Neutral Coll(2)Ln(4)(III) Clusters: Synthesis, Structure, and Magnetism
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Hexanuclear 3d-4f Neutral Coll(2)Ln(4)(III) Clusters: Synthesis, Structure, and Magnetism

机译：六核3d-4f中性Coll（2）Ln（4）（III）簇：合成，结构和磁性

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摘要

The sequential reaction of the multisite coordination ligand 6,6'-{(2-(dimethylamino)ethyl azanediyl)bis(methylene)}bis(2-methoxy-4-methylphenol) (LH2) with Ln(III) salts (Ln = Gd, Tb, Dy) and Co(ClO4)(2).6H(2)O in the presence of triethylamine and pivalic acid (pivH) in ambient conditions afforded a series of isostructural heterometallic hexanuclear Co-II/LnIII complexes with the general formula [CoII(2)Ln(4)(mu(3)-OH)(4)(L)(2)(piv)(8)(mu-OH2)].wCH(3)C.xCH(2)Cl(2).yCH(3)OH.zH(2)O (1: Ln = Gd, w = 5, x = 2, y = 0, z = 2; 2: Ln = Tb, w = 7, x = 4, y = 2, z = 0; 3: Ln = Dy; w = 4, x = 2, y = 2, z = 0). Compounds 1 and 3 crystallize in the monoclinic system, space group P2(1) (Z = 4), while compound 2 crystallizes in P2 (Z = 2). The hexanuclear core of the complexes comprises of a nonplanar arrangement of lanthanide ions bridged by two mu(3)-OH ligands. This tetranuclear motif is connected to the Co-II ions by two mu(3)-OH ligands. The overall structure contains four interlinked incomplete cubic subunits (two Co(II)Ln(2)(III)O(4) and two Ln(3)(III)O(4)) that are connected to each other by the sharing of two Ln(III) ions. The lanthanide centers are eight-coordinate (distorted trigonal-dodecahedron) and nine-coordinate (distorted monocapped square-antiprism), while the cobalt centers are six-coordinate (distorted octahedral). Magnetic measurement of the dysprosium analogue shows a slow magnetic relaxation.
机译：多位配位配体6,6'-{（2-（二甲基氨基）乙基氮杂二烷基）双（亚甲基）}双（2-甲氧基-4-甲基苯酚）（LH2）与Ln（III）盐的顺序反应（Ln = Gd，Tb，Dy）和Co（ClO4）（2）.6H（2）O在环境条件下三乙胺和新戊酸（pivH）的存在下提供了一系列同构异金属六核Co-II / LnIII配合物式[CoII（2）Ln（4）（mu（3）-OH）（4）（L）（2）（piv）（8）（mu-OH2）]。wCH（3）C.xCH（2） Cl（2）.yCH（3）OH.zH（2）O（1：Ln = Gd，w = 5，x = 2，y = 0，z = 2; 2：Ln = Tb，w = 7，x = 4，y = 2，z = 0; 3：Ln = Dy; w = 4，x = 2，y = 2，z = 0）。化合物1和3在单斜晶系统中结晶，空间群P2（1）/ n（Z = 4），而化合物2在P2 / n中结晶（Z = 2）。配合物的六核核心包含由两个mu（3）-OH配体桥接的镧系离子的非平面排列。该四核基序通过两个mu（3）-OH配体连接到Co-II离子。整体结构包含四个相互连接的不完整立方亚基（两个Co（II）Ln（2）（III）O（4）和两个Ln（3）（III）O（4）），它们通过共享两个Ln（III）离子。镧系元素中心是八坐标（扭曲的三角十二面体）和九坐标（扭曲的单峰方形反棱镜），而钴中心是六坐标（扭曲的八面体）。 analogue类似物的磁性测量显示缓慢的磁弛豫。

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