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化学学报
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化学学报 ›› 1996, Vol. 54 ›› Issue (6): 554-561. 上一篇    下一篇

研究论文

不同异构型的双铜配合物的结构、磁性和分子力学研究

程鹏;廖代正;阎世平;姜宗慧;王耕霖;王磊光;劳学军;姚心侃;王宏根;王国雄   

  1. 南开大学化学系;南开大学物理系;南开大学中心实验室;南京大学化学系
  • 发布日期:1996-06-15

Structural, magnetic and molecular mechanics studies on dicopper(Ⅱ) complexes with different tautomers

CHENG PENG;LIAO DAIZHENG;YAN SHIPING;JIANG ZONGHUI;WANG GENGLIN;WANG LEIGUANG;LAO XUEJUN;YAO XINKAN;WANG HONGGEN;WANG GUOXIONG   

  • Published:1996-06-15

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以2, 6-二甲酰-4-甲基苯酚双缩苯甲酰肼(H3L)为双核配体, 合成并表征了外源桥为N3^-的酮式双铜配合物[Cu2(H2L)(μ-N3)](ClO4)2.1/2C2H5OH(1)和酮醇混合式双铜配合物[Cu2(HL)(μ-N3)(ClO4)(C2H5OH)(H2O)](2)。2的晶体属于单斜晶系, 空间群P21/c, 晶胞参数: a=1.0967(4), b=0.7684(2),c=3.5724(7)nm; β=90.08(2)°; V=3.0103nm^3, Z=4, Dc=1.61g/cm^3;μ=15.66cm^-^1, F(000)=1488。最终的偏差因子R=0.083和Rw=0.088。对配合物在4~300K的磁化率数据分析表明, 铜离子间存在中等强度的反铁磁相互作用,交换参数(2J)分别为-86.8cm^-^1(1)和-132.4cm^-^1(2)。本文兼用分子力学和量子化学计算讨论了互变异构体对磁交换作用的的影响。

关键词: 苯酚 P, 红外分光光度法, 元素分析, 晶体结构, 铜络合物, 互变异构, 磁性, 分子力学, 苯甲酰肼

Two dicopper(Ⅱ) complexes, [Cu2(H2L)(μ-N3)](ClO4)2.1/2C2H5OH(1) and [Cu2(HL)(μ-N3)(ClO4)(C2H5OH)(H2O)](2), have been synthesized and characterized, where H3L is the binucleating ligand 2, 6-diformyl-4- methylphenol di(benzoylhydrazone). The crystal structure of 2 has been determined. Crystal data for 2 are monoclinic, space group P21/c, a=1.0967(4)nm, b=0.7684(2)nm, c=3.5724(7)nm, β=90.08(2)°, V=3.0103nm^3, Z=4, Dc=1.61g.cm^-^3, μ=15.66cm^-^1, F(000)=1488. The final R and Rw values are 0.083 and 0.088, respectively. The analysis of variable-temperature (4~300K) magnetic susceptibility data indicates that a medium antiferromagnetic interaction occured between copper(Ⅱ) ions. The exchange parameters (2J) are -86.8cm^-^1 for 1 and -132.4cm^-^1 for 2, respectively. The effect of tautomeric isomeride on magnetic interaction was discussed by molecular mechanics and CNDO/2 methods.

Key words: PHENOL P, INFRARED SPECTROPHOTOMETRY, ELEMENTAL ANALYSIS, CRYSTAL STRUCTURE, COPPER COMPLEX, TAUTOMERISM, MAGNETISM, MOLECULAR MECHANICS, BENZOYL HYDRAZINE

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