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

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

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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

Funding

The authors thank Hasselt University and the University of Namur for continuing financial support (BOF Ph.D. scholarships JD and TC). BC and WM thank the Research Foundation‐Flanders (FWO) for support through projects G087718N, G0D1521N, I006320N, GOH3816NAUHL, and the Scientific Research Community (WOG) ‘Supramolecular Chemistry and Materials’ (W000620N). The calculations were performed on the computers of the ‘Consortium des équipements de Calcul Intensif (CÉCI)’ ( http://www.ceci‐hpc.be ), including those of the ‘UNamur Technological Platform of High‐Performance Computing (PTCI)’ ( http://www.ptci.unamur.be ), for which we gratefully acknowledge financial support from the FNRS‐FRFC, the Walloon Region, and the University of Namur (Conventions No. 2.5020.11, GEQ U.G006.15, U.G018.19, 1610468, and RW/GEQ2016). The authors thank Hasselt University and the University of Namur for continuing financial support (BOF Ph.D. scholarships JD and TC). BC and WM thank the Research Foundation-Flanders (FWO) for support through projects G087718N, G0D1521N, I006320N, GOH3816NAUHL, and the Scientific Research Community (WOG) ?Supramolecular Chemistry and Materials? (W000620N). The calculations were performed on the computers of the ?Consortium des ?quipements de Calcul Intensif?(C?CI)? (http://www.ceci-hpc.be), including those of the ?UNamur Technological Platform of High-Performance Computing (PTCI)? (http://www.ptci.unamur.be), for which we gratefully acknowledge financial support from the FNRS-FRFC, the Walloon Region, and the University of Namur (Conventions No. 2.5020.11, GEQ U.G006.15, U.G018.19, 1610468, and RW/GEQ2016).

Keywords

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

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