Disperse black 9 based π-extented imine derivatives (HL1-HL3) and their Cu(II) and Pt(II) complexes were prepared and characterized by the analytical and spectroscopic methods. Single crystals of the Disperse black 9 and its π-extented imine derivatives (HL1-HL3) were obtained and their solid-state structures were investigated by X-ray diffraction studies. The photoluminescence and UV–vis spectra of the ligands and their metal complexes were investigated as both in the solid state and solution. Based on the emission spectra of the compounds, the 1931 CIE (x, y) chromaticity coordinates were investigated. The π-extention of Disperse black 9 as well as complexation with Cu(II) and Pt(II) ions resulted in the red shift in the emission spectra. The redox potentials of the synthesized compounds were investigated in the 100–1000 mVs−1 scan rate ranges via cycling voltammetry. Finally, the anticancer activity studies of the ligands and their metal complexes were investigated and the metal complexes have higher biological activities than the free ligands.