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Title: Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C 70 -Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium

Ultrafast photoinduced electron transfer (PIET) dynamics of a C 70-encapsulated bisporphyrin covalent organic polyhedron hybrid (C 70@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, R EE (2.8 Å), without the aid of covalent bonds. Sub-picosecond PIET (T ET ≤ 0.4 ps) and very slow charge recombination (T CR ≈ 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 C 70@COP-5 complex.
Authors:
 [1] ; ORCiD logo [2] ; ORCiD logo [3] ; ORCiD logo [4] ;  [3] ; ORCiD logo [5] ;  [6] ; ORCiD logo [7]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States). Chemistry and Nanoscience Center; Univ. of Colorado, Boulder, CO (United States). Dept. of Chemistry and Biochemistry
  2. Chonnam National Univ., Gwangju (South Korea). Dept. of Chemistry
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States). National Bioenergy Center
  5. Univ. of Colorado, Boulder, CO (United States). Dept. of Chemistry and Biochemistry
  6. National Renewable Energy Lab. (NREL), Golden, CO (United States). Chemistry and Nanoscience Center; Univ. of Colorado, Boulder, CO (United States). Dept. of Chemistry and Biochemistry; Univ. of Colorado, Boulder, CO (United States). Renewable and Sustainable Energy Inst.
  7. National Renewable Energy Lab. (NREL), Golden, CO (United States). Chemistry and Nanoscience Center
Publication Date:
Report Number(s):
NREL/JA-5900-67704
Journal ID: ISSN 0002-7863
Grant/Contract Number:
AC36-08GO28308; AC02-06CH11357; DMR-1055705
Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 12; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; photoinduced electron transfer; PIET; dynamics; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1351666
Alternate Identifier(s):
OSTI ID: 1350023; OSTI ID: 1351544

Ortiz, Michael, Cho, Sung, Niklas, Jens, Kim, Seonah, Poluektov, Oleg G., Zhang, Wei, Rumbles, Garry, and Park, Jaehong. Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C70 -Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium. United States: N. p., Web. doi:10.1021/jacs.7b00220.
Ortiz, Michael, Cho, Sung, Niklas, Jens, Kim, Seonah, Poluektov, Oleg G., Zhang, Wei, Rumbles, Garry, & Park, Jaehong. Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C70 -Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium. United States. doi:10.1021/jacs.7b00220.
Ortiz, Michael, Cho, Sung, Niklas, Jens, Kim, Seonah, Poluektov, Oleg G., Zhang, Wei, Rumbles, Garry, and Park, Jaehong. 2017. "Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C70 -Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium". United States. doi:10.1021/jacs.7b00220.
@article{osti_1351666,
title = {Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C70 -Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium},
author = {Ortiz, Michael and Cho, Sung and Niklas, Jens and Kim, Seonah and Poluektov, Oleg G. and Zhang, Wei and Rumbles, Garry and Park, Jaehong},
abstractNote = {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 (TET ≤ 0.4 ps) and very slow charge recombination (TCR ≈ 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.},
doi = {10.1021/jacs.7b00220},
journal = {Journal of the American Chemical Society},
number = 12,
volume = 139,
place = {United States},
year = {2017},
month = {3}
}