Excited-state and photoelectrochemical behavior of pyrene-linked phenyleneethynylene oligomer

An oligophenyleneethynylene (OPE), 1,4-bis(phenyleneethynyl)-2,5-bis(hexyloxy)benzene (2), is coupled with pyrene to extend the conjugation and allow its use as a light-harvesting molecule [Py-OPE (1)]. The absorption and emission maxima of 1 are red-shifted compared to those of 2. Similar differences in the singlet and triplet excited-state properties are evident. The fluorescence yield of 2 in toluene is 0.53, which is slightly less than the value for the parent OPE (2) of 0.66. The excited singlet and triplet of 1 as characterized from transient absorption spectroscopy exhibit lifetimes of 1.07 ns and 4.0 micros, respectively, in toluene. When 1 was cast as a film on a glass electrode (OTE) and excited with a 387-nm laser pulse, we observed the formation of excitons that decayed within a few picoseconds. When 1 was cast as a film on a SnO2-modified conducting glass electrode (OTE/SnO2), a small fraction of excitons dissociated to produce a long-lived charge-separated state. The role of the SnO2 interface in promoting charge separation was inferred from the photoelectrochemical measurements. Under visible light excitation, the OTE/SnO2 electrode was capable of generating photocurrent (approximately 0.25 mA/cm2) with an incident photon conversion efficiency (IPCE) of approximately 6%.