论文部分内容阅读
报道了配体N-(二茂铁基甲基)-1,4,7-氮杂-9-冠-3(L1)和N-(二茂钌基甲基)-1,4,7-氮杂-9-冠-3(L2)的Co(Ⅲ)和Fe(Ⅲ)配合物1～4的合成及电化学性质.配合物[Co(Ⅲ)_2(L1)_2(AcO)_2(OH)](ClO_4)(Ⅰ)_2(1)的晶体结构显示这些配合物具有线型排列的四金属中心结构.电化学研究表明:在这些配合物中,客体金属离子通过分子片断的电子传递作用使二茂金属的金属中心的氧化电位发生正移动.同时,不同二茂金属的取代效应也使相同客体金属离子的氧化电位不同.在两个二茂金属之间由于被大环1,4,7-氮杂-9-冠-3(tacn)和客体金属离子M~(3+)构成的配位部分所分隔没有相互作用,而由μ-AcO~-和μ-OH~-所桥联的两个客体金属离子之间却存在着相互耦合,以致在电化学循环过程中观察到了混合价电化学产物的存在.
The ligands N- (ferrocenylmethyl) -1,4,7-aza-9-crown-3 (L1) and N- (lodocentylmethyl) -1,4,7- Synthesis and Electrochemical Properties of Co (Ⅲ) and Fe (Ⅲ) Complexes 1 ~ 4 with Aza-9-crown- OH)] (ClO_4) (I) _2 (1) shows that these complexes have a linear arrangement of tetra-metal center structure.Electrochemical studies show that in these complexes, the guest metal ions through the molecular fragment electron transfer The role of the metallocene metal center oxidation potential positive shift at the same time, different metallocene substitution effect also makes the same guest metal ion oxidation potential difference between the two metallocenes by the macrocyclic 1,4 7-aza-9-crown-3 (tacn) and the guest metal ions M ~ (3+) constitute the coordination part of the separation without interaction, and by μ-AcO ~ - and μ-OH ~ The two guest metal ions in the couple are coupled to each other so that the presence of mixed valence chemical products is observed during electrochemical cycling.