Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C70-Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium

Michael Ortiz; Sung Cho; Jens Niklas; Seonah Kim; Oleg G. Poluektov; Wei Zhang; Garry Rumbles; Jaehong Park

doi:10.1021/jacs.7b00220

Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C₇₀-Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium

Michael Ortiz, Sung Cho, Jens Niklas, Seonah Kim, Oleg G. Poluektov, Wei Zhang, Garry Rumbles, Jaehong Park

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

57 Scopus citations

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, R_EE (2.8 Å), without the aid of covalent bonds. Sub-picosecond PIET (τ_ET ≤ 0.4 ps) and very slow charge recombination (τ_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 C₇₀@COP-5 complex.

Original language	English
Pages (from-to)	4286-4289
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	139
Issue number	12
DOIs	https://doi.org/10.1021/jacs.7b00220
State	Published - 29 Mar 2017

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

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10.1021/jacs.7b00220

Cite this

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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 {\AA}), 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.",

author = "Michael Ortiz and Sung Cho and Jens Niklas and Seonah Kim and Poluektov, {Oleg G.} and Wei Zhang and Garry Rumbles and Jaehong Park",

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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

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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