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Published on: August 18, 2017
Symmetry-Breaking Charge Separation in a Chiral Bis(perylenediimide) Probed at Ensemble and Single-Molecule Levels
Philip Daniel Maret1, Devika Sasikumar1, Ebin Sebastian1
1School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Maruthamala P.O., Vithura, Thiruvananthapuram, Kerala 695551, India.
Abstract:
Chiral molecular assemblies exhibiting symmetry-breaking charge separation (SB-CS) are potential candidates for the development of chiral organic semiconductors. Herein, we explore the excited-state dynamics of a helically chiral perylenediimide bichromophore (Cy-PDI2) exhibiting SB-CS at the ensemble and single-molecule levels. Solvent polarity-tunable interchromophoric excitonic coupling in chiral Cy-PDI2 facilitates the interplay of SB-CS and excimer formation in the ensemble domain. Analogous to the excited-state dynamics of Cy-PDI2 at the ensemble level, single-molecule fluorescence lifetime traces of Cy-PDI2 depicted long-lived off-states characteristic of the radical ion pair-mediated dark states. The discrete electron transfer and charge separation dynamics in Cy-PDI2 at the single-molecule level are governed by the distinct influence of the local environment. The present study aims at understanding the fundamental excited-state dynamics in chiral organic bichromophores for designing efficient chiral organic semiconductors and applications toward charge transport materials.
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