Design, synthesis and photophysical studies of phenylethynyl-bridged phthalocyanine-fullerene dyads

A zinc and a free base phthalocyanine-fulleropyrrolidine dyad in which the chromophores are linked by a phenylethynyl group have been prepared using a new synthetic route, and their photoelectrochemical properties have been investigated. The zinc dyad is readily soluble in a variety of solvents, and its spectroscopic properties have been determined in toluene and benzonitrile. In toluene, excitation of the zinc phthalocyanine is followed by rapid establishment of an equilibrium between the phthalocyanine and fullerene excited states. These excited states decay mainly to the ground state and the respective triplet states. The fullerene triplet then transfers its energy to form the phthalocyanine triplet. About 20% of the phthalocyanine excited states lead to formation of a charge-separated state. In benzonitrile, the same decay pathways are observed, but photoinduced electron transfer is much faster, and generates the charge separated state with a quantum yield of ≥ 85%. The charge separated state has a lifetime of 2.8 ns in toluene and 94 ps in benzonitrile.