Photochromic Control of Photoinduced Electron Transfer. Molecular Double-Throw Switch

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Abstract
A molecular double-throw switch that employs a photochromic moiety to direct photoinduced electron transfer from an excited state donor down either of two pathways has been prepared. The molecular triad consists of a free base porphyrin (P) linked to both a C60 electron acceptor and a dihydroindolizine (DHI) photochrome. Excitation of the porphyrin moiety of DHI−P−C60 results in photoinduced electron transfer with a time constant of 2.3 ns to give the DHI−P•+−C60•- charge-separated state with a quantum yield of 82%. UV (366 nm) light photoisomerizes the DHI moiety to the betaine (BT) form, which has a higher reduction potential than DHI. Excitation of the porphyrin of BT−P−C60 is followed by photoinduced electron transfer with a time constant of 56 ps to produce BT•-−P•+−C60 in 99% yield. Isomerization of BT−P−C60 back to DHI−P−C60 may be achieved with visible light, or thermally. Thus, photoinduced charge separation originating from the porphyrin is reversibly directed down either of two different pathways by photoisomerization of the dihydroindolizine. The switch may be cycled many times.