Halogen Mediated Self-assembly of Three Mixed Valent Cu(Ⅰ)/Cu(Ⅱ) Complexes

Reaction of the ligand dmpt（dmpt=6,7-dimethylbenzo[f][1,10]phenanthroline）with CuCl;afforded mixed valent Cu（Ⅰ）/Cu（Ⅱ） discrete tetranuclear complexes[Cu（Ⅱ）Cl;（dmpt）Cu（Ⅰ）Cl]（1）,while the reaction of ligand dppz（dppz = dipyrido[3,2-a:20,30-c]phenazine） with divalent halogen copper salt CuX;（X=Cl,Br） gave one-dimensional chain mixed valent Cu（Ⅰ）/Cu（Ⅱ） complexes [Cu（Ⅱ）Cl;（dppz）Cu（Ⅰ）Cl];（2） and discrete mixed valent Cu（Ⅰ）/Cu（Ⅱ）complexes [Cu（Ⅱ）Br;（dppz）(DMF)Cu（Ⅰ）Br]（3）. Complex 2 consists of a one-dimensional chain-dppzC u（Ⅱ）-Clμ;-Cu（Ⅰ）-Cl-dppzC u（Ⅱ）-Clμ;-Cu（Ⅰ）-with Cu（Ⅱ） and Cu（Ⅰ） atoms linked together by chloride anion. Complex 3 is a discrete complex,which is the same as complexes 1 and 2 involving two different copper valent Cu（Ⅰ） and Cu（Ⅱ）. The Cu（Ⅰ） ion presents a pseudo-trihedral geometry,while the Cu（Ⅱ） ion presents a slightly distorted square-pyramidal geometry. This fact proved that halogen ions play a vital role in the assembly procedure. Our research results demonstrate the structural diversification that can be achieved by halogen ions mediated. Moreover,halogen ions-mediated self-assembly may provide useful information for further design of compounds with novel structures and properties.