Heavy-Atom-Free Bay-Substituted Perylene Diimide Donor-Acceptor Photosensitizers

Jasper Deckers, Tom Cardeynaels, Laurence Lutsen, Benoît Champagne, Wouter Maes

Research output: Contribution to journalArticlepeer-review

Abstract

Perylene diimide (PDI) dyes are extensively investigated because of their favorable photophysical characteristics for a wide range of organic material applications. Fine-tuning of the optoelectronic properties is readily achieved by functionalization of the electron-deficient PDI scaffold. Here, we present four new donor-acceptor type dyads, wherein the electron donor units – benzo[1,2-b : 4,5-b’]dithiophene, 9,9-dimethyl-9,10-dihydroacridine, dithieno[3,2-b : 2’,3’-d]pyrrole, and triphenylamine-are attached to the bay-positions of the PDI acceptor. Intersystem crossing occurs for these systems upon photoexcitation, without the aid of heavy atoms, resulting in singlet oxygen quantum yields up to 80 % in toluene solution. Furthermore, this feature is retained when the system is directly irradiated with energy corresponding to the intramolecular charge-transfer absorption band (at 639 nm). Geometrical optimization and (time-dependent) density functional theory calculations afford more insights into the requirements for intersystem crossing such as spin-orbit coupling, dihedral angles, the involvement of charge-transfer states, and energy level alignment.

Original languageEnglish
Pages (from-to)1488-1496
Number of pages9
JournalChemPhysChem
Volume22
Issue number14
Early online date25 May 2021
DOIs
Publication statusPublished - 16 Jul 2021

Keywords

  • charge transfer
  • intersystem crossing
  • perylene diimides
  • photosensitizers
  • singlet oxygen

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