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 CuCl2 afforded mixed valent Cu(I)/Cu(II) discrete tetranuclear complexes [Cu(II)Cl2(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 CuX2 (X = Cl, Br) gave one-dimensional chain mixed valent Cu(I)/Cu(II) complexes [Cu(II)Cl2(dppz)Cu(I)Cl]n (2) and discrete mixed valent Cu(I)/Cu(II) complexes [Cu(II)Br2(dppz)(DMF)Cu(I)Br] (3). Complex 2 consists of a one-dimensional chain -dppzCu(II)-Clμ2-Cu(I)-Cl-dppzCu(II)-Clμ2-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.