Porphyrin Nanowire Bundles for Efficient Photoconductivity, Photoemission, and Generation of Singlet Oxygens toward Photodynamic Therapy

Energy released from an accelerated high-energy single/cluster particle triggers solid-state polymerization and cross-linking reactions of porphyrin-based pi-conjugated monomers within a nanometer-scaled one-dimensional spatial area along the ion trajectory, resulting in the formation of an insoluble nanowire with a precise diameter and length. The nanowires are isolated by the development process-immersion of the irradiated film in organic solvents-and their shape and geometry are clearly characterized by atomic force microscopy. The obtained nanowire bundles, reflecting precisely the number of incident particles, show characteristic absorption spectra originating from porphyrin chromophores without significant degradation of the molecular cores. These porphyrin-based nanowires can be further functionalized into metallocomplexes by immersing the nanowires into solutions containing metal ion sources. The remarkable finding on the monomer structural parameters is that terminal alkyne groups are preferentially reacted and thus highly effective as a monomer structure for the present single particle-triggered linear polymerization method. The porphyrin-based nanowires show much higher photoconductivity than the precursor porphyrin films and enhanced fluorescence on silver nanoparticle layers via surface plasmon resonance. The porphyrin nanowires serve as photosensitizers mediating the generation of singlet oxygens, which is attractive for the use as a controlled nanosystem toward photocatalysis and photodynamic therapy.