title: Hole transfer in a C-shaped molecule: conformational freedom versus solvent-mediated coupling.
abstract: The electronic coupling matrix elements attending the charge separation reactions of a C-shaped molecule containing an excited pyrene as the electron acceptor and a dimethylaniline as the donor are determined in aromatic, ether, and ester solvents. Band shape analyses of the charge-transfer emission spectra (CT --> S(0)) provide values of the reaction free energy, the solvent reorganization energy, and the vibrational reorganization energy in each solvent. The free energy for charge separation in benzene and toluene solvents is independently determined from the excited state equilibrium established between the locally excited pyrene S(1) state and the charge-transfer state. Analyses of the charge separation kinetics using the spectroscopically determined reorganization energies and reaction free energies indicate that the electronic coupling is solvent independent, despite the presence of a cleft between the donor and acceptor. Hence, solvent molecules are not involved in the coupling pathway. The orientations of the donor and acceptor units, relative to the spacer, are not rigidly constrained, and their torsional motions decrease solvent access to the cleft. Generalized Mulliken-Hush calculations show that rotation of the pyrene group about the bond connecting it to the spacer greatly modulates the magnitude of through-space coupling between the S(1) and CT states. The relationship between the torsional dynamics and the electron-transfer dynamics is discussed.
authors.affiliation: Contribution from the Department of Chemistry, Brown University, Providence, Rhode Island 02912, USA.
authors.forename: Jocelyn M
authors.initials: JM
authors.lastname: Nadeau
authors.forename: Min
authors.initials: M
authors.lastname: Liu
authors.forename: David H
authors.initials: DH
authors.lastname: Waldeck
authors.forename: Matthew B
authors.initials: MB
authors.lastname: Zimmt