title: Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C70-Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium.
abstract: Ultrafast photoinduced electron transfer (PIET) dynamics of a C70-encapsulated bisporphyrin covalent organic polyhedron hybrid (C70@COP-5) is studied in a nonpolar toluene medium with fluorescence and transient absorption spectroscopies. This structurally rigid donor (D)-acceptor (A) molecular hybrid offers a new platform featuring conformationally predetermined cofacial D-A orientation with a fixed edge-to-edge separation, REE(2.8 Å), without the aid of covalent bonds. Sub-picosecond PIET (τET≤ 0.4 ps) and very slow charge recombination (τCR≈ 600 ps) dynamics are observed. The origin of these dynamics is discussed in terms of enhanced D-A coupling (V = 675 cm-1) and extremely small reorganization energy (λ ≈ 0.18 eV), induced by the intrinsic structural rigidity of the C70@COP-5 complex.
authors.forename: Michael
authors.initials: M
authors.lastname: Ortiz
authors.affiliation: Department of Chemistry, Chonnam National University , Gwangju 500-757, South Korea.
authors.forename: Sung
authors.identifier: 0000-0002-6499-9947
authors.initials: S
authors.lastname: Cho
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Jens
authors.identifier: 0000-0002-6462-2680
authors.initials: J
authors.lastname: Niklas
authors.forename: Seonah
authors.identifier: 0000-0001-9846-7140
authors.initials: S
authors.lastname: Kim
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Oleg G
authors.initials: OG
authors.lastname: Poluektov
authors.forename: Wei
authors.identifier: 0000-0002-5491-1155
authors.initials: W
authors.lastname: Zhang
authors.forename: Garry
authors.initials: G
authors.lastname: Rumbles
authors.forename: Jaehong
authors.identifier: 0000-0002-0509-3934
authors.initials: J
authors.lastname: Park