TY - JOUR
T1 - Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C70-Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium
AU - Ortiz, Michael
AU - Cho, Sung
AU - Niklas, Jens
AU - Kim, Seonah
AU - Poluektov, Oleg G.
AU - Zhang, Wei
AU - Rumbles, Garry
AU - Park, Jaehong
N1 - Funding Information:
This work was supported by the Solar Photochemistry Program of the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Contract Number DE-AC36-08GO28308 to NREL and Contract DE-AC02-06CH11357 at Argonne National Laboratory (J.N. and O.G.P.). The synthesis of COP-5 was supported by an NSF grant to W.Z. (DMR-1055705). The theoretical calculations were supported by the National Institute of Supercomputing and Network/Korea Institute of Science and Technology Information with supercomputing resources including technical support.
PY - 2017/3/29
Y1 - 2017/3/29
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.7b00220
DO - 10.1021/jacs.7b00220
M3 - Article
C2 - 28287707
AN - SCOPUS:85016304205
VL - 139
SP - 4286
EP - 4289
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 12
ER -