Electron-transfer, complete, photo-induced

Acetylchloride is a trapping agent that allows the reaction to go completion, transforming the product into a less oxidizable compound.The results of other reactions between indole (57) and substituted cyclohexa-1,3-dienes show that the photo-induced Diels-Alder reaction is almost completely regioselective. In the absence of 59 the cycloaddition did not occur the presence of [2+2] adducts was never detected. Experimental data support the mechanism illustrated in Scheme 4.14. The intermediate 57a, originated from bond formation between the indole cation radical and 58, undergoes a back-electron transfer to form the adduct 60 trapped by acetyl chloride. 

We have previously shown that when PPV is self-assembled with specific electronically active polyanions such as poly(thiophene acetic acid) (PTAA) or sulfonated fiillerenes (S-C60 )(7), the photoluminescence of the PPV is essentially completely quenched by the polyanion. The mechanism of this quenching is believed to be due to a photoinduc electron transfer process taking place between the excited PPV and the adjacent electroactive polyanion molecules. The quenching process, in this case, is not associated with a Forster type energy transfer since in both cases, the required spectral overlap of a donor emission band with an acceptor absorption band is not fulfilled. In addition, photo-induced electron transfer processes have previously been confirmed in PPV/C60 systems and can be exploited to fabricate thin film photovoltaic devices (77). In order to mediate this electron transfer process, we have constructed multilayer heterostructures in which the PPV donor and the polyanion electron acceptor are separated from each other with electronically inert spacer layers of known thickness. In addition to allowing studies of the electron transfer process, such structures provide important insights into the thermal stability of the multilayer structure. The "spacers" used in this study were bilayers of SPS/PAH with an experimentally determined bilayer thickness of 30 +/-5 A. 

The photo-induced electron-transfer reactions of the type delineated above are completely reversible, and result in no net chemical transformation of the molecular complex or radical pair. This chemical unreactivity is due to the facility of the back-electron transfer reaction — the application of light serving merely to generate a photostationary state, i.e. 

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