Hexanuclear 3d–4f Neutral CoII2LnIII4 Clusters: Synthesis, Structure, and Magnetism
Hexanuclear 3d–4f Neutral CoII2LnIII4 Clusters: Synthesis, Structure, and Magnetism
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DOI：
10.1021/acs.cgd.5b00588
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发表时间：
2015-05
影响因子：
3.8
通讯作者：
Joydeb Goura;A. Chakraborty;J. P. Walsh;F. Tuna;V. Chandrasekhar
中科院分区：
文献类型：
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作者：
Joydeb Goura;A. Chakraborty;J. P. Walsh;F. Tuna;V. Chandrasekhar
多位配体6，6 ′-{（2-（二甲氨基）乙基氮烷二基）双（亚甲基）}双（2-甲氧基-4-甲基苯酚）（LH 2）与Ln III盐（Ln = Gd，Tb，Dy）和Co（ClO 4）2·6 H2O在三乙胺和新戊酸（pivH）存在下合成了一系列同结构异金属六核Co Ⅱ/Ln Ⅲ配合物[Co Ⅱ 2Ln 4（μ3-OH）4（L）2（piv）8（μ-OH 2）]·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属于单斜晶系，空间群为P21/n（Z = 4），而化合物2属于P2/n（Z = 2）。配合物的六核由两个μ3-OH配体桥联的镧系离子的非平面排列组成。该四核基序通过两个μ3-OH配体连接到CoII离子。整体结构包含四个相互连接的不完全立方亚基（两个CoIIInIII 2 O 4和两个LnIII 3 O 4）。
The sequential reaction of the multisite coordination ligand 6,6′-{(2-(dimethylamino)ethyl azanediyl)bis(methylene)}bis(2-methoxy-4-methylphenol) (LH2) with LnIII salts (Ln = Gd, Tb, Dy) and Co(ClO4)2·6H2O in the presence of triethylamine and pivalic acid (pivH) in ambient conditions afforded a series of isostructural heterometallic hexanuclear CoII/LnIII complexes with the general formula [CoII2Ln4(μ3-OH)4(L)2(piv)8(μ-OH2)]·wCH3C·xCH2Cl2·yCH3OH·zH2O (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 P21/n (Z = 4), while compound 2 crystallizes in P2/n (Z = 2). The hexanuclear core of the complexes comprises of a nonplanar arrangement of lanthanide ions bridged by two μ3-OH ligands. This tetranuclear motif is connected to the CoII ions by two μ3-OH ligands. The overall structure contains four interlinked incomplete cubic subunits (two CoIILnIII2O4 and two LnIII3O4) tha...