Abstract Complexes with the formula, Cu(\overset1O·C6H4·\overset2CH=N–Ph–X)Cl, where Ph-X is a mono- or disubstituted phenyl group, were prepared. A dimeric structure was postulated for these complexes based on the observed subnormal magnetic moments and the chemical formula. For these complexes, a linear relation was observed to exist between the magnetic moments, μeff25°C, and the d–d band positions, \ ildenumax. The d–d bands of the dimeric complexes with o-substituents appeared at shorter wavelengths than those with m- or p-substituents irrespective of the polar nature of the substituents. A similar ortho-effect was also observed for the magnetic moments; complexes with o-substituents were observed to have smaller moment values than those with m- or p-substituents. The oryho-effect was also observed in the d–d bands of the monomeric bis-complexes Cu(\overset1O·C6H4·\overset2CH=N–Ph–X)2 and their d–d bands when X=o-substituents appeared at shorter wavelengths than those with m- or p-substituents. These ortho-effects decreased for the solution spectra of the monomeric complexes.