title: Energy and Electron Transfer Dynamics within a Series of Perylene Diimide/Cyclophane Systems.
abstract: Artificial photosynthetic systems for solar energy conversion exploit both covalent and supramolecular chemistry to produce favorable arrangements of light-harvesting and redox-active chromophores in space. An understanding of the interplay between key processes for photosynthesis, namely light-harvesting, energy transfer, and photoinduced charge separation and the design of novel, self-assembling components capable of these processes are imperative for the realization of multifunctional integrated systems. We report our investigations on the potential of extended tetracationic cyclophane/perylene diimide systems as components for artificial photosynthetic applications. We show how the selection of appropriate heterocycles, as extending units, allows for tuning of the electron accumulation and photophysical properties of the extended tetracationic cyclophanes. Spectroscopic techniques confirm energy transfer between the extended tetracationic cyclophanes and perylene diimide is ultrafast and quantitative, while the heterocycle specifically influences the energy transfer related parameters and the acceptor excited state.
authors.affiliation: Melville Laboratory for Polymer Synthesis, Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge, CB2 1EW, U.K.
authors.forename: Seán T J
authors.initials: ST
authors.lastname: Ryan
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.|Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: Ryan M
authors.initials: RM
authors.lastname: Young
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: James J
authors.initials: JJ
authors.lastname: Henkelis
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: Nema
authors.initials: N
authors.lastname: Hafezi
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: Nicolaas A
authors.initials: NA
authors.lastname: Vermeulen
authors.affiliation: School of Engineering and Science, Jacobs University Bremen , Campus Ring 1, 28759 Bremen, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Hennig
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: Edward J
authors.initials: EJ
authors.lastname: Dale
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.|Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: Yilei
authors.initials: Y
authors.lastname: Wu
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.|Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: Matthew D
authors.initials: MD
authors.lastname: Krzyaniak
authors.affiliation: Melville Laboratory for Polymer Synthesis, Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge, CB2 1EW, U.K.
authors.forename: Athan
authors.initials: A
authors.lastname: Fox
authors.affiliation: School of Engineering and Science, Jacobs University Bremen , Campus Ring 1, 28759 Bremen, Germany.
authors.forename: Werner M
authors.initials: WM
authors.lastname: Nau
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.|Argonne-Northwestern Solar Energy Research (ANSER) Center, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: Michael R
authors.initials: MR
authors.lastname: Wasielewski
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: J Fraser
authors.initials: JF
authors.lastname: Stoddart
authors.affiliation: Melville Laboratory for Polymer Synthesis, Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge, CB2 1EW, U.K.
authors.forename: Oren A
authors.initials: OA
authors.lastname: Scherman