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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Dinuclear copper(II) complexes of a novel 3-(aminomethyl)naphthoquinone Mannich base: Synthesis, structural, magnetic and electrochemical studies
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Dinuclear copper(II) complexes of a novel 3-(aminomethyl)naphthoquinone Mannich base: Synthesis, structural, magnetic and electrochemical studies

机译：新型3-（氨基甲基）萘醌曼尼希碱的双核铜（II）配合物：合成，结构，磁性和电化学研究

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摘要

A novel versatile tridentate 3-(aminomethyl)naphthoquinone proligand, 3-[N-(2-pyridylmethyl)aminobenzyl]-2-hydroxy-1,4-naphthoquinone (HL), was obtained from the Mannich reaction of 2-hydroxy-1,4-naphthoquinone (Lawsone) with 2-aminomethylpyridine (amp) and benzaldehyde. The reactions of HL with CuCl_2·2H_2O yielded two novel dinuclear copper(II) complexes, [Cu(L)(H_2O)(μ-Cl)Cu(L)Cl] (1b), [CuCl(L)(μ-Cl) Cu(amp)Cl] (2) and a polymeric compound, [Cu(L)Cl)]_n (1a), whose relative yields were sensitive to temperature, reagents concentration and presence of base. The crystalline structures of 1b and 2 were determined by X-ray diffraction studies. The two copper atoms in complex 1b are connected by a single chloro bridge with a Cu?Cu separation of 4.1342(8) and Cu(1)-Cl(1)-Cu(2) angle of 109.31(4)°. In complex 2 the two copper atoms are held together by a chloro and a naphthalen-2-olate bridges [Cu(1)-Cl(2)-Cu(2) and Cu(1)-O(1)-Cu(2) angles being 83.31(3) and 109.70(9)°, respectively, and the Cu?Cu separation, 3.3476(9)?]. As expected, variable-temperature magnetic susceptibility measurements of complex 1b showed weak antiferromagnetic intramolecular coupling between the copper(II) centers, with J = -5.7 cm~(-1), and evidenced for complex 2 strong antiferromagnetic coupling, with J ～ -120 cm~(-1). Furthermore, the magnetic behaviour of compound 1a suggested an infinite 1D coordination polymeric structure in which the copper(II) centers are connected by Cl-Cu-Cl bridges. Solution data (UV-Vis spectroscopy and cyclic voltammetry) indicated structural changes of 2 and 1a in CH_3CN, and evidenced conversion of polymer 1a into dimer 1b.
机译：从2-羟基-1的曼尼希反应中获得了新型的多功能三齿3-（氨基甲基）萘醌配体3- [N-（2-吡啶基甲基）氨基苄基] -2-羟基-1,4-萘醌（HL）。 ，4-萘醌（Lawsone）与2-氨基甲基吡啶（amp）和苯甲醛。 HL与CuCl_2·2H_2O的反应产生了两种新型的双核铜（II）配合物，[Cu（L）（H_2O）（μ-Cl）Cu（L）Cl]（1b），[CuCl（L）（μ-Cl ）Cu（amp）Cl]（2）和高分子化合物[Cu（L）Cl）] _ n（1a），其相对产率对温度，试剂浓度和碱的存在敏感。 1b和2的晶体结构通过X射线衍射研究确定。络合物1b中的两个铜原子通过一个氯桥连接，铜间距为4.1342（8），Cu（1）-Cl（1）-Cu（2）角为109.31（4）°。在络合物2中，两个铜原子通过氯和萘-2-油酸酯桥[Cu（1）-Cl（2）-Cu（2）和Cu（1）-O（1）-Cu（2）结合在一起角分别为83.31（3）和109.70（9）°，而Cu2Cu间距为3.3476（9）？]。不出所料，配合物1b的变温磁化率测量结果表明，铜（II）中心之间的弱反铁磁分子内耦合，J = -5.7 cm〜（-1），并证明了配合物2的强反铁磁耦合，J〜- 120厘米〜（-1）此外，化合物1a的磁性表现出无限的一维配位聚合物结构，其中铜（II）中心通过Cl-Cu-Cl桥连接。溶液数据（紫外-可见光谱和循环伏安法）表明CH_3CN中2和1a的结构发生了变化，并证明了聚合物1a转化为二聚体1b。

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