title: Through-Solvent Tunneling in Donor-Bridge-Acceptor Molecules Containing a Molecular Cleft.
abstract: Photoinduced electron transfer is used to investigate the solvent-mediated electron tunneling between electron donor and acceptor groups in polar solvents. Bis-peptide scaffolds are used to control the spatial positioning of electron donor and acceptor groups and create a molecular cleft. The photoinduced electron transfer is studied for two different cleft sizes, and the electronic coupling is found to be controlled by the nature of the solvent and the ability of the molecular cleft to accommodate it, as well as interact directly with it. These studies demonstrate the importance of electron tunneling through nonbonded contacts and reveal a strategy for examining such tunneling pathways in polar solvents.
authors.affiliation: Chemistry Department, University of Pittsburgh , Pittsburgh Pennsylvania 15260, United States.
authors.forename: B M
authors.initials: BM
authors.lastname: Graff
authors.affiliation: Chemistry Department, University of Pittsburgh , Pittsburgh Pennsylvania 15260, United States.
authors.forename: D N
authors.initials: DN
authors.lastname: Lamont
authors.affiliation: Chemistry Department, Temple University , Philadelphia, Pennsylvania, United States.
authors.forename: M F L
authors.initials: MF
authors.lastname: Parker
authors.affiliation: Chemistry Department, University of Pittsburgh , Pittsburgh Pennsylvania 15260, United States.
authors.forename: B P
authors.initials: BP
authors.lastname: Bloom
authors.affiliation: Chemistry Department, Temple University , Philadelphia, Pennsylvania, United States.
authors.forename: C E
authors.initials: CE
authors.lastname: Schafmeister
authors.affiliation: Chemistry Department, University of Pittsburgh , Pittsburgh Pennsylvania 15260, United States.
authors.forename: D H
authors.initials: DH
authors.lastname: Waldeck