TY - JOUR
T1 - Reversible Symmetry-Breaking Charge Separation in a Series of Perylenediimide Cyclophanes
AU - Coleman, Adam F.
AU - Chen, Michelle
AU - Zhou, Jiawang
AU - Shin, Jae Yoon
AU - Wu, Yilei
AU - Young, Ryan M.
AU - Wasielewski, Michael R.
N1 - Funding Information:
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).
Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/5/14
Y1 - 2020/5/14
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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U2 - 10.1021/acs.jpcc.0c02382
DO - 10.1021/acs.jpcc.0c02382
M3 - Article
AN - SCOPUS:85085945470
VL - 124
SP - 10408
EP - 10419
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 19
ER -