Abstract

The nanofabrication of molecular semiconductors for the construction of molecular photoelectronic devices is an important of research; to this end, we have constructed porphyrin polymers possessing a tailor-made structure. In this paper, we report the photoelectronic function of the porphyrin polymers connected by oligothienyl bridges. One-dimensional porphyrin polymers with various lenghts of oligothienyl bridge in the axial direction were synthesized by the electrochemical polymerization of symmetrical bis(oligothienylalkoxy) phosphorus(V)-porphyrin. The conductivity of the polymer was strongly enhanced by photoirradiation, indicating photoinduced carrier formation. The layered sandwich cell of the polymer with polybithiophene showed electric rectifying properties in the dark. Interestingly, photovoltage and photo-current were observed on photoirradiation. On the basis of these results, a microscopic polymer junction chip was constructed. Two-dimensional porphyrin polymers containing oligothienyl bridges in the lateral direction were prepared by similar electrochemical oxidation of meso-tetrakis (oligothienyl) porphyrin metal complexes and were fabricated as layered diodes.

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