Self-assembly of novel tris(p-carboxyphenyl) porphyrin monomer and its copolymers with acrylamide in aqueous media

The novel porphyrin monomer 5-(4-acryloyloxylphenyl)-10,15,20-tris(4-carboxyphenyl)porphyrinate zinc(II) (ZnAOTCPP) and its corresponding sodium salt (ZnAOTCPP-Na) were synthesized. The latter compound exhibited a new band in excitation spectra due to formation of porphyrin aggregates in water, which were derived from its surface-activity when the concentration was higher than its critical association concentration (CAC). The porphyrins were copolymerized with acrylamide (AM) to prepare water-soluble copolymers with random and micro-blocky structures, which all displayed very new absorption and fluorescence emission bands in the long wavelength region compared with the porphyrin monomer. Furthermore, the micro-blocky copolymer exhibited an additional new absorption band at even longer wavelength region compared with the random copolymer. The experimental results and analysis showed that the porphyrin units in the random copolymer chains self-assembled to form porphyrin association complexes by hydrophobic association and π–π stacking interactions, and covalent restrictions of polymer chains in the micro-blocky copolymer.

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► The synthesis of novel tricarboxylphenyl porphyrin monomer and its corresponding sodium salt.
► The preparation of random copolymer and micro-blocky copolymer with porphyrins and acrylamide.
► The self-assembly of sodium salt of porphyrin monomer and copolymers in water.
► The characteristic absorption of porphyrin assemblies exhibiting at long wavelength region.
► The mimic light-harvesting system of water-soluble polymer containing porphyrins.