Photoinitiated long-lived charge separation with near-unity quantum yield in donor-acceptor1-acceptor2 systems for artificial photosynthesis

Won Sik Han; Brad S. Veldkamp; Scott M. Dyar; Samuel W. Eaton; Michael R. Wasielewski

doi:10.1016/j.tet.2017.06.021

Photoinitiated long-lived charge separation with near-unity quantum yield in donor-acceptor₁-acceptor₂ systems for artificial photosynthesis

Won Sik Han, Brad S. Veldkamp, Scott M. Dyar, Samuel W. Eaton, Michael R. Wasielewski^*

^*Corresponding author for this work

Chemistry

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

2 Scopus citations

Abstract

We report the synthesis and photophysical characterization of isomeric donor-acceptor₁-acceptor₂ (D-A₁-A₂) triads each comprising a perylene donor (D) connected by a xylene bridge to a naphthalene-1,8-dicarboximide primary acceptor (NMI, A₁) that is, in turn, covalently linked to a naphthalene-1,4:5,8-bis(dicarboximide) secondary acceptor (NDI, A₂) through a benzene ring at its ortho, meta or para positions (Per-Xy-NMI-x-NDI). Selective photoexcitation of Per produces both Per^+• and NDI^‒• simultaneously with time constants of ∼50 ps in benzonitrile and ∼80 ps in toluene with a >98% yield. This is much faster than expected for single-step electron transfer from ^1*Per to NDI and is consistent with a two-step mechanism, ^1*Per-Xy-NMI-x-NDI → Per^+•-Xy-NMI^‒•-x-NDI → Per^+•-Xy-NMI-x-NDI^‒•, in which the second step is much faster than the first step. In addition, preserving long-lived charge separation in these systems is found to depend on inhibiting charge recombination by a triplet radical ion pair recombination pathway.

Original language	English (US)
Pages (from-to)	4925-4935
Number of pages	11
Journal	Tetrahedron
Volume	73
Issue number	33
DOIs	https://doi.org/10.1016/j.tet.2017.06.021
State	Published - 2017

Keywords

Donor-acceptor
Photochemistry
Radical pairs
Transient absorption spectroscopy

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tet.2017.06.021

Cite this

@article{2d240b37dbc34aa79dac06c9bd724654,

title = "Photoinitiated long-lived charge separation with near-unity quantum yield in donor-acceptor1-acceptor2 systems for artificial photosynthesis",

abstract = "We report the synthesis and photophysical characterization of isomeric donor-acceptor1-acceptor2 (D-A1-A2) triads each comprising a perylene donor (D) connected by a xylene bridge to a naphthalene-1,8-dicarboximide primary acceptor (NMI, A1) that is, in turn, covalently linked to a naphthalene-1,4:5,8-bis(dicarboximide) secondary acceptor (NDI, A2) through a benzene ring at its ortho, meta or para positions (Per-Xy-NMI-x-NDI). Selective photoexcitation of Per produces both Per+• and NDI‒• simultaneously with time constants of ∼50 ps in benzonitrile and ∼80 ps in toluene with a >98% yield. This is much faster than expected for single-step electron transfer from 1*Per to NDI and is consistent with a two-step mechanism, 1*Per-Xy-NMI-x-NDI → Per+•-Xy-NMI‒•-x-NDI → Per+•-Xy-NMI-x-NDI‒•, in which the second step is much faster than the first step. In addition, preserving long-lived charge separation in these systems is found to depend on inhibiting charge recombination by a triplet radical ion pair recombination pathway.",

keywords = "Donor-acceptor, Photochemistry, Radical pairs, Transient absorption spectroscopy",

author = "Han, {Won Sik} and Veldkamp, {Brad S.} and Dyar, {Scott M.} and Eaton, {Samuel W.} and Wasielewski, {Michael R.}",

note = "Funding Information: This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, an Office of Basic Energy Sciences, DOE under grant no. DE-FG02-99ER14999. B.S.V. is supported by the Department of Energy Office of Science Graduate Fellowship Program (DOE SCGF), made possible in part by the American Recovery and Reinvestment Act of 2009, administered by ORISE-ORAU under contract no. DE-AC05-06OR23100. S.W.E. acknowledges support from the International Materials Institute for Solar Energy and Environment funded by National Science Foundation under grant no. DMR-0843962. W.S.H. acknowledges funding from National Research Foundation of Korea Grant funded by the Korean Government (NRF-2011-C00053) and funding from Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (2014R1A1A1005982). Publisher Copyright: {\textcopyright} 2017 Elsevier Ltd",

year = "2017",

doi = "10.1016/j.tet.2017.06.021",

language = "English (US)",

volume = "73",

pages = "4925--4935",

journal = "Tetrahedron",

issn = "0040-4020",

publisher = "Elsevier Limited",

number = "33",

}

TY - JOUR

T1 - Photoinitiated long-lived charge separation with near-unity quantum yield in donor-acceptor1-acceptor2 systems for artificial photosynthesis

AU - Han, Won Sik

AU - Veldkamp, Brad S.

AU - Dyar, Scott M.

AU - Eaton, Samuel W.

AU - Wasielewski, Michael R.

N1 - Funding Information: This work was supported by the Chemical Sciences, Geosciences, and Biosciences Division, an Office of Basic Energy Sciences, DOE under grant no. DE-FG02-99ER14999. B.S.V. is supported by the Department of Energy Office of Science Graduate Fellowship Program (DOE SCGF), made possible in part by the American Recovery and Reinvestment Act of 2009, administered by ORISE-ORAU under contract no. DE-AC05-06OR23100. S.W.E. acknowledges support from the International Materials Institute for Solar Energy and Environment funded by National Science Foundation under grant no. DMR-0843962. W.S.H. acknowledges funding from National Research Foundation of Korea Grant funded by the Korean Government (NRF-2011-C00053) and funding from Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning (2014R1A1A1005982). Publisher Copyright: © 2017 Elsevier Ltd

PY - 2017

Y1 - 2017

N2 - We report the synthesis and photophysical characterization of isomeric donor-acceptor1-acceptor2 (D-A1-A2) triads each comprising a perylene donor (D) connected by a xylene bridge to a naphthalene-1,8-dicarboximide primary acceptor (NMI, A1) that is, in turn, covalently linked to a naphthalene-1,4:5,8-bis(dicarboximide) secondary acceptor (NDI, A2) through a benzene ring at its ortho, meta or para positions (Per-Xy-NMI-x-NDI). Selective photoexcitation of Per produces both Per+• and NDI‒• simultaneously with time constants of ∼50 ps in benzonitrile and ∼80 ps in toluene with a >98% yield. This is much faster than expected for single-step electron transfer from 1*Per to NDI and is consistent with a two-step mechanism, 1*Per-Xy-NMI-x-NDI → Per+•-Xy-NMI‒•-x-NDI → Per+•-Xy-NMI-x-NDI‒•, in which the second step is much faster than the first step. In addition, preserving long-lived charge separation in these systems is found to depend on inhibiting charge recombination by a triplet radical ion pair recombination pathway.

AB - We report the synthesis and photophysical characterization of isomeric donor-acceptor1-acceptor2 (D-A1-A2) triads each comprising a perylene donor (D) connected by a xylene bridge to a naphthalene-1,8-dicarboximide primary acceptor (NMI, A1) that is, in turn, covalently linked to a naphthalene-1,4:5,8-bis(dicarboximide) secondary acceptor (NDI, A2) through a benzene ring at its ortho, meta or para positions (Per-Xy-NMI-x-NDI). Selective photoexcitation of Per produces both Per+• and NDI‒• simultaneously with time constants of ∼50 ps in benzonitrile and ∼80 ps in toluene with a >98% yield. This is much faster than expected for single-step electron transfer from 1*Per to NDI and is consistent with a two-step mechanism, 1*Per-Xy-NMI-x-NDI → Per+•-Xy-NMI‒•-x-NDI → Per+•-Xy-NMI-x-NDI‒•, in which the second step is much faster than the first step. In addition, preserving long-lived charge separation in these systems is found to depend on inhibiting charge recombination by a triplet radical ion pair recombination pathway.

KW - Donor-acceptor

KW - Photochemistry

KW - Radical pairs

KW - Transient absorption spectroscopy

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U2 - 10.1016/j.tet.2017.06.021

DO - 10.1016/j.tet.2017.06.021

M3 - Article

AN - SCOPUS:85020876140

SN - 0040-4020

VL - 73

SP - 4925

EP - 4935

JO - Tetrahedron

JF - Tetrahedron

IS - 33

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