Synthesis and structure of vinylporphyrin metal complexes and their copolymerization. Spectral luminescence properties of Zn copolymers in solution

Vinylporphyrins containing one vinyl group at the pyrrole or benzene ring a nd their complexes with Cu2+ and Zn2+ have been obtained by the Wittig reac tion. The compounds obtained were characterized by physicochemical methods. X-ray diffraction analysis of 5-(4-vinylphenyl)-10,15,20-triphenylporphyri n has been carried out. It is likely that the inclusion of the vinyl group is accompanied by weak electron effects on the macrocycles. The radical-ind uced copolymerization of meso-tetraphenylporphyrin monomers with the vinyl group in a benzene or pyrrole ring and their copper and zinc complexes with styrene and methacrylate was studied. Porphyrin comonomers decrease the ov erall polymerization rate and the number-average molecular weight of the pr oducts formed compared with the weight of polystyrene obtained under simila r conditions. The main reasons for termination of chain growth by vinylporp hyrins were revealed and some quantitative parameters of these reactions we re obtained. IR and electronic absorption spectra of porphyrin-containing c opolymers are discussed. According to the ESR spectra, the copper-containin g centres in the copolymers are fairly remote from each other, and the meta l-containing polymeric systems are magnetically dilute. The spectral lumine scence properties of solutions of zinc 5-(4-vinylphenyl)-10,15,20-triphenyl porphyrin-methyl methacrylate copolymers with various contents of porphyrin groups were studied. It was shown that a new long-wave band appears in the absorption spectra of the copolymers, the intensity of which depends on th e copolymer composition, and the quantum yield of fluorescence decreases wi th increasing molar fraction of porphyrin groups. Copyright (C) 2000 John W iley & Sons, Ltd.