Reversible Symmetry-Breaking Charge Separation in a Series of Perylenediimide Cyclophanes

Adam F. Coleman; Michelle Chen; Jiawang Zhou; Jae Yoon Shin; Yilei Wu; Ryan M. Young; Michael R. Wasielewski

doi:10.1021/acs.jpcc.0c02382

Reversible Symmetry-Breaking Charge Separation in a Series of Perylenediimide Cyclophanes

Adam F. Coleman, Michelle Chen, Jiawang Zhou, Jae Yoon Shin, Yilei Wu, Ryan M. Young^*, Michael R. Wasielewski

^*Corresponding author for this work

Chemistry

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

64 Scopus citations

Abstract

Excited-state symmetry-breaking charge separation (SB-CS) can offer an efficient pathway to solar energy capture and conversion. We synthesized a series of 1,6,7,12-tetrakis(4-t-butylphenoxy)perylene(3,4:9,10)bis(dicarboximide) cyclophane dimers with m-xylylene, p-xylylene, and 4,4′-diyldimethane-1,1′-biphenyl spacers and studied them with steady-state and time-resolved optical spectroscopies. Photoinduced SB-CS occurs in all three cyclophanes in CH₂Cl₂, with the SB-CS rate decreasing as the interchromophore distance is increased. Time-resolved emission spectroscopy and kinetic modeling reveal that the charge-separated state exists in pseudoequilibrium with the excited state prior to decay. Notably, the meta-spaced cyclophane also undergoes SB-CS in toluene within ∼100 ps, despite the lack of charge stabilization by the low dielectric constant solvent. These results demonstrate that SB-CS can occur across long distances and in weakly polar environments, which offers the possibility of harnessing SB-CS for solar energy capture and conversion.

Original language	English (US)
Pages (from-to)	10408-10419
Number of pages	12
Journal	Journal of Physical Chemistry C
Volume	124
Issue number	19
DOIs	https://doi.org/10.1021/acs.jpcc.0c02382
State	Published - May 14 2020

Funding

The authors thank Jonathan Schultz for useful discussion regarding DFT calculations. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-FG02-99ER14999. This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN).

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Energy
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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title = "Reversible Symmetry-Breaking Charge Separation in a Series of Perylenediimide Cyclophanes",

abstract = "Excited-state symmetry-breaking charge separation (SB-CS) can offer an efficient pathway to solar energy capture and conversion. We synthesized a series of 1,6,7,12-tetrakis(4-t-butylphenoxy)perylene(3,4:9,10)bis(dicarboximide) cyclophane dimers with m-xylylene, p-xylylene, and 4,4′-diyldimethane-1,1′-biphenyl spacers and studied them with steady-state and time-resolved optical spectroscopies. Photoinduced SB-CS occurs in all three cyclophanes in CH2Cl2, with the SB-CS rate decreasing as the interchromophore distance is increased. Time-resolved emission spectroscopy and kinetic modeling reveal that the charge-separated state exists in pseudoequilibrium with the excited state prior to decay. Notably, the meta-spaced cyclophane also undergoes SB-CS in toluene within ∼100 ps, despite the lack of charge stabilization by the low dielectric constant solvent. These results demonstrate that SB-CS can occur across long distances and in weakly polar environments, which offers the possibility of harnessing SB-CS for solar energy capture and conversion.",

author = "Coleman, {Adam F.} and Michelle Chen and Jiawang Zhou and Shin, {Jae Yoon} and Yilei Wu and Young, {Ryan M.} and Wasielewski, {Michael R.}",

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AU - Young, Ryan M.

AU - Wasielewski, Michael R.

PY - 2020/5/14

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N2 - Excited-state symmetry-breaking charge separation (SB-CS) can offer an efficient pathway to solar energy capture and conversion. We synthesized a series of 1,6,7,12-tetrakis(4-t-butylphenoxy)perylene(3,4:9,10)bis(dicarboximide) cyclophane dimers with m-xylylene, p-xylylene, and 4,4′-diyldimethane-1,1′-biphenyl spacers and studied them with steady-state and time-resolved optical spectroscopies. Photoinduced SB-CS occurs in all three cyclophanes in CH2Cl2, with the SB-CS rate decreasing as the interchromophore distance is increased. Time-resolved emission spectroscopy and kinetic modeling reveal that the charge-separated state exists in pseudoequilibrium with the excited state prior to decay. Notably, the meta-spaced cyclophane also undergoes SB-CS in toluene within ∼100 ps, despite the lack of charge stabilization by the low dielectric constant solvent. These results demonstrate that SB-CS can occur across long distances and in weakly polar environments, which offers the possibility of harnessing SB-CS for solar energy capture and conversion.

AB - Excited-state symmetry-breaking charge separation (SB-CS) can offer an efficient pathway to solar energy capture and conversion. We synthesized a series of 1,6,7,12-tetrakis(4-t-butylphenoxy)perylene(3,4:9,10)bis(dicarboximide) cyclophane dimers with m-xylylene, p-xylylene, and 4,4′-diyldimethane-1,1′-biphenyl spacers and studied them with steady-state and time-resolved optical spectroscopies. Photoinduced SB-CS occurs in all three cyclophanes in CH2Cl2, with the SB-CS rate decreasing as the interchromophore distance is increased. Time-resolved emission spectroscopy and kinetic modeling reveal that the charge-separated state exists in pseudoequilibrium with the excited state prior to decay. Notably, the meta-spaced cyclophane also undergoes SB-CS in toluene within ∼100 ps, despite the lack of charge stabilization by the low dielectric constant solvent. These results demonstrate that SB-CS can occur across long distances and in weakly polar environments, which offers the possibility of harnessing SB-CS for solar energy capture and conversion.

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Reversible Symmetry-Breaking Charge Separation in a Series of Perylenediimide Cyclophanes

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