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

✍ Scribed by Anatolii D. Pomogailo; Vladimir F. Razumov; Igor’ S. Voloshanovskii

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 197 KB
• Volume: 04
• Category: Article
• ISSN: 1088-4246
• DOI: 10.1002/(sici)1099-1409(200001/02)4:1<45::aid-jpp195>3.0.co;2-m

✦ Synopsis

Vinylporphyrins containing one vinyl group at the pyrrole or benzene ring and their complexes with Cu ^2+^ and Zn ^2+^ have been obtained by the Wittig reaction. The compounds obtained were characterized by physicochemical methods. X-ray diffraction analysis of 5-(4-vinylphenyl)-10,15,20-triphenylporphyrin 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-induced 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 overall polymerization rate and the number-average molecular weight of the products formed compared with the weight of polystyrene obtained under similar conditions. The main reasons for termination of chain growth by vinylporphyrins were revealed and some quantitative parameters of these reactions were obtained. IR and electronic absorption spectra of porphyrin-containing copolymers are discussed. According to the ESR spectra, the copper-containing centres in the copolymers are fairly remote from each other, and the metal-containing polymeric systems are magnetically dilute. The spectral luminescence properties of solutions of zinc 5-(4-vinylphenyl)-10,15,20-triphenylporphyrin–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 the copolymer composition, and the quantum yield of fluorescence decreases with increasing molar fraction of porphyrin groups.