Synthesis Of Porphyrin Polymers Via "Click" Reaction

Porphyrins are always one of the hottest research topics in chemical catalysis, photoluminescence materials, molecular targeted drugs. Porphyrin polymers have better properties in energy and electron transfer than monomers, which can be applied in synthsis of nonlinear optical materials and molecular devices. In this paper, we synthesized porphyrin polymers via"Click"reaction. Monomer 5,15-diynylporphyrin was first synthesized and then using diazide as bridging agent for the synthesis of novel porphyrin polymers by"Click"reaction. The key studies are listed below.(1) Reacted with 5-phenyldipyrromethane and 4-(2-propynyloxy)benzaldehyd for synthesis of 5,15-bis[4-(prop-2-ynyloxy)phenyl]-10,20-diphenylporphyrin and its metal derivative by MacDonald method. Synthesis of 5-[4-(prop-2-ynyloxy)phenyl]- 10,15,20-triphenylporphyrin by Adler method. 1,4-diazidobenzene, 4,4'-diazidobi- phenyl, 4,4'-bis(azidomethyl)biphenyl were obtained by diazotization and nucleophilic substitution of NaN3, These compounds were characterized by FT-IR, and 1H NMR.(2) Four novel porphyrin polymers (P1, P2, P3, Zn-P1) were prepared by using 5,15-bis[4-(prop-2-ynyloxy)phenyl]-10,20-diphenylporphyrin and its metal derivative as monomers, diazide as bridging agents via Cu(I)-catalyzed and thermal"Click"reaction. These polymers were characterized by FT-IR, 1H NMR and GPC. The photophysical properties of porphyrin monomers and polymers were characterized by UV-vis and fluorescence spectrophotometer. P1, P2, P3 exhibit an intense Soret band at 420 nm together with four weak Q-bands at 515, 551, 590, 648 nm. Zn-P1 exhibit a Soret band at 427 nm, and two weak Q-bands. The polymer thin films absorption spectrum of P1, Zn-P1 show a stronger Q-bands, wider Soret band. Fluorescence emission spectra of P1, P2, P3 show the maximum emission peak at 655 nm and a shoulder at 719 nm, wuich bule-shift compared with the maximum emission peak of Zn-P1 at 609 nm and a shoulder at 660 nm.