title: Photoinitiated charge transport through pi-stacked electron conduits in supramolecular ordered assemblies of donor-acceptor triads.
abstract: Photochemical electron donor-acceptor triads having an aminopyrene primary donor (APy) and a p-diaminobenzene secondary donor (DAB) attached to either one or both imide nitrogen atoms of a perylene-3,4:9,10-bis(dicarboximide) (PDI) electron acceptor were prepared to give DAB-APy-PDI and DAB-APy-PDI-APy-DAB. In toluene, both triads are monomeric, but in methylcyclohexane, they self-assemble into ordered helical heptamers and hexamers, respectively, in which the PDI molecules are pi-stacked in a columnar fashion, as evidenced by small- and wide-angle X-ray scattering. Photoexcitation of these supramolecular assemblies results in rapid formation of DAB(+*)-PDI(-*) spin-polarized radical ion pairs having spin-spin dipolar interactions, which show that the average distance between the two radical ions is much larger in the assemblies (31 A) than it is in their monomeric building blocks (23 A). This work demonstrates that electron hopping through the pi-stacked PDI molecules is fast enough to compete effectively with charge recombination (40 ns) in these systems, making these materials of interest as photoactive assemblies for artificial photosynthesis and organic photovoltaics.
authors: Department of Chemistry and Argonne-Northwestern Solar Energy Research Center, Northwestern University, Evanston, Illinois 60208-3113, USA.
authors: Joseph E
authors: JE
authors: Bullock
authors: Raanan
authors: R
authors: Carmieli
authors: Sarah M
authors: SM
authors: Mickley
authors: Josh
authors: J
authors: Vura-Weis
authors: Michael R
authors: MR
authors: Wasielewski