Cu(Ⅰ) and Cu (Ⅱ) helical complexes formed with oligobipyridine ligand  

作　　者：舒谋海 付有君 孙为银 唐雯霞 张文剑 段春迎 

出　　处：《Science China Chemistry》1999年第5期501-510,共10页中国科学（化学英文版）

基　　金：Project supported by the National Natural Science Foundation of China (Grant No. 29601003).

摘　　要：A new asymmetric oligobipyridine ligand, l-( 5'-methyl-2, 2'-bipyridin-5-yl )-2-( 6'-methyl-2, 2'-bipyridin-6-yl)ethane (L) , in which the bipyridine units are bridged by CH2CH2 at 5 ,6'-position has been synthesized. The ligand L reacts with Cu(Ⅰ) and Cu(Ⅱ) ions giving double-stranded helical complexes [Cu12L2] (ClO4)2· Et2O(l) and [CuⅡ2L2(OH)(H2O)][C1O4]3(2) , respectively. Complexes 1 and 2 were characterized by X-ray diffraction analyses, ES-MS, ESR and cyclic voltammetry, etc. Differing from the oligobipyridine ligands bridged by CH2CH2 at 6,6'-or 5,5'-position, the ligand L not only forms a double-stranded helicate with Cu(Ⅱ) ion, but also gives a double-stranded helicate with Cu(Ⅰ) ion. The results show that the linkage mode of the spacer group to the bipyridine units exerts a gr at impact on the formation of helix.A new asymmetric oligobipyridine ligand, 1-（5’-methyl-2, 2’-bipyridin-5-yl）-2-（6’-methyl-2, 2’-bipyridin-6-yl）ethane （L）, in which the bipyridine units are bridged by CH₂CH₂ at 5, 6’-position has been synthesized. The ligand L reacts with Cu（Ⅰ） and Cu（Ⅱ） ions giving double-stranded helical complexes [Cu₂^ⅠL₂] （ClO₄）₂·Et₂O （1） and [Cu₂^ⅡL₂ （OH） （H₂O）][ClO₄]₃（2）, respectively. Complexes 1 and 2 were characterized by X-ray diffraction analyses, ES-MS, ESR and cyclic voltammetry, etc. Differing from the oligobipyridine ligands bridged by CH₂CH₂ at 6,6’-or 5,5’-position, the ligand L not only forms a double-stranded helicate with Cu（Ⅰ） ion, but also gives a double-stranded helicate with Cu（Ⅱ） ion. The results show that the linkage mode of the spacer group to the bipyridine units exerts a great impact on the formation of helix.

关 键 词：HELIX copper complex SUPRAMOLECULE self-assembly crystal structure ELECTROSPRAY mass spectrometry. 

分 类 号：O641.4[理学—物理化学]