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Complex formation of two novel politopic mono- and bis- crown-containing 4-styryl bipyrydine 1 and 2 with Cd2+, Zn2+, Hg2+, Co2+, Fe2+, H+, Ba2+, Ca2+ in MeCN was studied by absorption and emission spectroscopy. Two binding centers of different nature in ligands 1 and 2 exhibit specific affinity to different metal cations. The crown ether moieties prefer to bind with alkaline and alkaline-earth metal cations resulting in hypsochromic shift of long wavelength absorption band. On the contrary bipyrydine moiety binds with heavy and transition metal ions leading to bathochromic shift of long wavelength absorption band.