Department of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata-700 032, India E-mail : c_r_sinha@yahoo.com Manuscript received 18 May 2006, accepted 26 May 2006 Zinc(II) complexes of 1-alkyl-2-(naphthyl-α/β-azo)imidazoles (azoimine function, -N=N-C=N-) and α/β-naphthyl-(2- pyridylmethylene)amine (diimine function, -N=C-C=N-) are described in this article. The complexcs arc spcctroscopically characterized (IR, UV-Vls, NMR). The composition of the complex depends on the counter ions used; the reaction of ZnCl2 with ligand gives tctrahedrol Zn(ligand)Cl2; Zn(NO3)2 prepares -O-NO2 coordinated octahedral [Zn(ligand)2(ONO2)2) compound while Zn(ClO4)2 isolates tetrahedral [Zn(ligand)2)(ClO4)2complex.Single crystal X-ray structure of [Zn(β-naphthyl- (2-pyridylmethylcnc)aminc)2(ONO2)2] has suggested coordination of O-NO2unit.Zinc(u)-diimine complexes arc luminescent while 7inc(II)-azoiminc system arc nonlumincsccnt. Emission is of ligand centered π-π* origin and of good quantum yield (reference to coumarin-120).