The chromophore in some bis azomethazine Schiff base complexes of nickel

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The effect of substitution on the chromophore in bis azomethazine Schiff base nickel complexes was examined by measuring the electronic spectra of a series of such complexes in chloroform solution. Solid-state spectra of the complexes were similar but less well defined than solution spectra but the definition could be improved by cooling KBr discs containing dispersed complexes to 8 K. On the basis of a CNDO molecular-orbital calculation, the nature of the orbitals likely to produce the observed spectra was defined and band assignments proposed by reference to experimental evidence. It would seem that the lowest energy bands are due to a series of transitions between orbitals which are located mainly on the nickel-to-oxygen bonds but which also contain an appreciable orbital contribution from the aromatic ring system.