双大环配体与铜双核配合物的合成、晶体结构和磁偶合性质

由新型双功能配体2,6-双(1,5,9-三氮杂环十二烷)-2,6-二甲基苯甲酸(L)与溴化铜在甲醇中反应得到新型铜双核配合物[Cu~2LBr~2]Br.3H~2O单晶。晶体结构分析表明:2个Cu(II)中心离子由配体L中的羧酸基团桥联;2个等价的Cu(II)中心离子均由双功能配体L的1,5,9-三氮杂环十二烷([12aneN~3)的3个氮原子和羧酸的1个氧原子及1个Br^-离子配位,并都处在三角双锥的配位环境中;分子内Cu...Cu双核间的距离为0.5884(6)nm。变温磁化率数据表明:在同一分子中的2个铜核之间存在反铁磁偶合作用(J=-22.49cm^-^1)。

Synthesis, crystal structure and magnetic properties of a new dicopper(II) complex with a bis(macrocyclic) ligand

A new binuclear copper(II) complex, [Cu~2LBr~2]Br.3H~2O, where L is a new binucleating macrocyclic ligand 2, 6-bis(1, 5, 9- triazacyclododecan-9-ylmethyl) benzoate, has been prepared and characterized by X-ray crystallography. Crystal data: monoclinic, space group P2~1/c, a=1.1666(2), b=1.3541(3), c=2.2750(5)nm, β=99.38 (3)ⅲ, Z=4. The binuclear copper(II) center ions are bridged by a μ - carboxyl group of L and separated by 0.5884nm. Both of the copper(II) ion centers are coordinated by three amine nitrogens of [12] aneN~3 subunit and one oxygen of the carboxyl group, as well as one bromide ion. The copper(II) ion is in the trigonal bipyramid environment. Variable temperature magnetic susceptibility studies indicate that three exists intramolecular antiferro-magnetic coupling (J=-22.49cm^- ^1) between the two copper(II) centers.