title: Dipole-mediated rectification of intramolecular photoinduced charge separation and charge recombination.
abstract: Controlling charge transfer at a molecular scale is critical for efficient light harvesting, energy conversion, and nanoelectronics. Dipole-polarization electrets, the electrostatic analogue of magnets, provide a means for "steering" electron transduction via the local electric fields generated by their permanent electric dipoles. Here, we describe the first demonstration of the utility of anthranilamides, moieties with ordered dipoles, for controlling intramolecular charge transfer. Donor-acceptor dyads, each containing a single anthranilamide moiety, distinctly rectify both the forward photoinduced electron transfer and the subsequent charge recombination. Changes in the observed charge-transfer kinetics as a function of media polarity were consistent with the anticipated effects of the anthranilamide molecular dipoles on the rectification. The regioselectivity of electron transfer and the molecular dynamics of the dyads further modulated the observed kinetics, particularly for charge recombination. These findings reveal the underlying complexity of dipole-induced effects on electron transfer and demonstrate unexplored paradigms for molecular rectifiers.
authors.affiliation: Department of Bioengineering, ‡Department of Biochemistry, §Department of Chemistry, and ∥Materials Science and Engineering Program, University of California , Riverside, California 92521, United States.
authors.forename: Duoduo
authors.initials: D
authors.lastname: Bao
authors.forename: Srigokul
authors.initials: S
authors.lastname: Upadhyayula
authors.forename: Jillian M
authors.initials: JM
authors.lastname: Larsen
authors.forename: Bing
authors.initials: B
authors.lastname: Xia
authors.forename: Boriana
authors.initials: B
authors.lastname: Georgieva
authors.forename: Vicente
authors.initials: V
authors.lastname: Nuñez
authors.forename: Eli M
authors.initials: EM
authors.lastname: Espinoza
authors.forename: Joshua D
authors.initials: JD
authors.lastname: Hartman
authors.forename: Michelle
authors.initials: M
authors.lastname: Wurch
authors.forename: Andy
authors.initials: A
authors.lastname: Chang
authors.forename: Chung-Kuang
authors.initials: CK
authors.lastname: Lin
authors.forename: Jason
authors.initials: J
authors.lastname: Larkin
authors.forename: Krystal
authors.initials: K
authors.lastname: Vasquez
authors.forename: Gregory J O
authors.initials: GJ
authors.lastname: Beran
authors.forename: Valentine I
authors.initials: VI
authors.lastname: Vullev
mesh_terms: D004579:Electron Transport; D004583:Electrons; D007700:Kinetics; D056004:Molecular Dynamics Simulation; D055672:Static Electricity; D013237:Stereoisomerism; D062367:ortho-Aminobenzoates / Q000737:chemistry*
chemical_list: D062367:ortho-Aminobenzoates; C000219:anthranilamide