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- W3019040524 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." @default.
- W3019040524 created "2020-05-01" @default.
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- W3019040524 date "2020-04-23" @default.
- W3019040524 modified "2023-10-16" @default.
- W3019040524 title "Reversible Symmetry-Breaking Charge Separation in a Series of Perylenediimide Cyclophanes" @default.
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- W3019040524 doi "https://doi.org/10.1021/acs.jpcc.0c02382" @default.
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