Supramolecular Photoreactor

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This project focused a biomimetic approach of artificial photosynthesis based on two-dimensional supramolecular assemblies. Charge transfer (CT) complexes are often used as a charge separation device in an artificial photosynthesis and photo conductive materials. Two-dimensional supramolecular assemblies.e.g. bilayr membranes and Langmuir-Blodgett films, are suitable candidates for designing CT complexes. Based on "pseudo crystal engineering" of bilayr membranes, we succeeded tailoring an intermolecular CT complex between a hydrophobic biphenyl moiety and a hydrophilic viologen head in an aqueous bilayr membrane.The hydrophilic viologen head and the hydrophobic aromatic segment of the adjacent molecule was expected to be closely packed in the tilted molecular orientation.A broad absorption band at 460nm attributed to a CT complex was observed in the aqueous bilayr solution of C12BphC5V2+, whereas a water solution of C8BphC10V2+ had no absorption in visible region. A long lived viologen radicals was also found on visible light irradiation of the CT complex. Langmuir-Blodgett films of C12BphC5V2+ prepared by the polyion complex technique on ITO electrodes clearly showed reversible redox reaction of the Viologen group and the LB film effectively mediated electrons from the electrode to a redox flavin enzyme, diaphorase. Photochemical reduction of diaphorase and NAD by the photochemically generated viologen radical was investigated.