Synthesis, electrochemical and magnetic properties of new macrocyclic copper(II) complexes derived from 2,6-diacetyl-4-4-methylphenol

Author： Zhan S-z. Miao Y. Li P. Yuan C-w.

Publisher： Springer Publishing Company

ISSN： 0340-4285

Source： Transition Metal Chemistry, Vol.24, Iss.3, 1999-06, pp. : 311-316

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Abstract

A series of binuclear macrocyclic copper(II) complexes [Cu2Lm,n](ClO4)2·xH2O have been prepared in which the two copper(II) ions are placed in two geometrically distinct co-ordination environments. The macrocycles with two 2,6-bis(iminomethyl)-4-methylphenol entities combined through two different lateral chains, –(–CH2–)–m and –(–CH2–)–n (m = 2 or 3, n = 2 to 5) were synthesized by stepwise cyclization. Cyclic voltammetry shows the presence of two reduction couples: CuIICuII CuICuII and CuIICuI CuICuI. The comproportionation constants, Kcom, for the mixed valence CuICuII complexes have been determined electrochemically. The Kcom value increases in the order of the macrocycles: (L2,2)2-<><><(l2,5)2- and=""><><(l3,5)2-. cryomagnetic="" investigations="" (80–300k)="" reveal="" a="" moderately="" strong="" antiferromagnetic="" spin="" exchange="" between="" the="" copper(ii)="" ions="" within="" each="" complex="" (j="-210" to="" -390="" cm-1).="">