The results of optical and NMR spectroscopy studies showed that crown containing styrylphenantrolines can form molecular assemblies in the presence of metal ions of different nature. The composition and structure of the assemblies can be controlled using the laws of complexation. It was found that zinc complexes with styrylphenantrolines are fluorescence ligands for metal cations that can coordinate to free crown ether fragments of the styrylphenan throline molecules.