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| - Nanoscale Organization of Chlorophyll a in Mesoporous Silica: Efficient Energy Transferand Stabilized Charge Separation as in Natural Photosynthesis
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| - Chlorophyll a molecules were adsorbed to mesoporous silica (FSM: folded-sheet mesoporous material) toform a chlorophyll−FSM conjugate capable of nanometer-scale interaction between chlorophyll a moleculesas seen in a living plant leaf. The chlorophyll a molecules introduced into nanopores of FSM-22 (with a porediameter of 4 nm) exhibited a red shift in the absorption peak and showed efficient excitation energy transferfrom the shorter to the longer wavelength forms as characterized by the fast transient phase of 38 ps detectedin the decay-associated spectrum (DAS) analysis of the fluorescence decay. Illumination of the chlorophyll−FSM-22 conjugate with visible light generated a stable chlorophyll a cation radical in the electron spin resonance(ESR) measurement, although the illumination of free chlorophyll a in solution produced almost no cationsignal. The physiological function of the chlorophyll−FSM conjugate intercalated with ruthenium oxide (RuO2)was explored as chlorophyll−FSM exhibited the photoinduced ability to catalyze the reduction of DCIP (anelectron carrier). The mesoporous silica−chlorophyll conjugate in an appropriate system thus produced asolar energy conversion system enabling fast energy transfer and stable charge separation, presumably byproducing the appropriate interaction of pigments as occurs in living photosynthetic apparatus.
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