Two New Diphenoxo-Bridged Discrete Dinuclear CuIIGdIII Compounds with Cyclic Diimino Moieties: Syntheses, Structures, and Magnetic Properties
Two New Diphenoxo-Bridged Discrete Dinuclear CuIIGdIII Compounds with Cyclic Diimino Moieties: Syntheses, Structures, and Magnetic Properties
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DOI：
10.1002/ejic.200400858
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发表时间：
2005-04
影响因子：
2.3
通讯作者：
Rajesh Koner;Gene-Hsiang Lee;Yu Wang;Ho‐Hsiang Wei;Sasankasekhar Mohanta
中科院分区：
文献类型：
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作者：
Rajesh Koner;Gene-Hsiang Lee;Yu Wang;Ho‐Hsiang Wei;Sasankasekhar Mohanta
两个希夫碱室配体 H 2 L 1 和 H 2 L 2 分别衍生自 3-乙氧基水杨醛与 1,2-二氨基环己烷和邻苯二胺的缩合，已被用来分离两个二苯氧桥联离散双核 Cu I I Gd I I I 配合物，[Cu I I (H 2 O)-L 1 Gd I I I (NO 3 ) 3 ] (3) 和 [Cu I I L 2 Gd I I I (NO 3 ) 3 ] (4)。这是关于源自分区席夫碱配体与环状二胺的 3d-4f 化合物的第一份报告。化合物 3 和 4 分别在三斜 Pi 和斜方 Pna2(1) 空间群中结晶，晶胞参数如下 - 3：a = 8.8713(2) A, b = 12.8399(3) A, c = 14.0067(3) A, a = 80.6649(5)°, β = 77.4059(5)°, γ = 76.8879(5)°，Z = 2； 4：a = 9.2210(1) A，b = 16.5407(2) A，c = 19.9248(4) A，Z = 4。结构分析表明两者都是离散的双核配合物。在3中，一个水分子与铜(II)离子配位，形成方形锥体配位几何形状，而在4中铜(II)中心的几何形状是方形平面。在这两种配合物中，钆(III) 中心具有O 1 0 配位环境。与预期相反，虽然N 2 O 2 空腔为4中的铜(II)中心提供了更好的平面环境，但配合物3中的桥接部分比4或大多数先前报道的例子中的桥接部分更平坦（两个CuO 2 Gd平面之间的二面角：3为2.1°，4为7.1°）。变温和变场磁测量表明，两种配合物中的金属中心都是铁磁耦合的（J 值：3 为 6.3 cm - 1，4 为 5.4 cm - 1；H = -2JS C u .S G d ）。有趣的是，配合物 3 在相关化合物中表现出最强的铁磁相互作用。
Two Schiff base compartmental ligands, H 2 L 1 and H 2 L 2 , derived from the condensation of 3-ethoxysalicylaldehyde with 1,2-diaminocyclohexane and orthophenylenediamine, respectively, have been utilized to isolate two diphenoxo-bridged discrete dinuclear Cu I I Gd I I I complexes, [Cu I I (H 2 O)-L 1 Gd I I I (NO 3 ) 3 ] (3) and [Cu I I L 2 Gd I I I (NO 3 ) 3 ] (4). This is the first report on the 3d-4f compounds derived from compartmental Schiff base ligands with cyclic diamines. The compounds 3 and 4 crystallize in the triclinic Pi and orthorhombic Pna2(1) space groups, respectively, with the following unit cell parameters - 3: a = 8.8713(2) A, b = 12.8399(3) A, c = 14.0067(3) A, a = 80.6649(5)°, β = 77.4059(5)°, γ = 76.8879(5)°, and Z = 2; 4: a = 9.2210(1) A, b = 16.5407(2) A, c = 19.9248(4) A, and Z = 4. Structural analysis reveals that both are discrete dinuclear complexes. In 3, one water molecule is coordinated to the copper(II) ion to result in a square-pyramidal coordination geometry, while the geometry of the coppe(II) center in 4 is square planar. In both complexes, the gadolinium(III) center has an O 1 0 coordination environment. In contrast to expectation, although the N 2 O 2 cavity affords a better planar environment for the copper(II) center in 4, the bridging moiety in complex 3 is more planar than that in 4 or in most of the previously reported examples (the dihedral angle between two CuO 2 Gd planes: 2.1° for 3 and 7.1° for 4). Variable-temperature and variable-field magnetic measurements reveal that the metal centers in both the complexes are ferromagnetically coupled (J values: 6.3 cm - 1 for 3 and 5.4 cm - 1 for 4; H = -2JS C u .S G d ). Interestingly, complex 3 exhibits strongest ferromagnetic interaction among the related compounds.