TY - JOUR
T1 - Heavy-Atom-Free Bay-Substituted Perylene Diimide Donor-Acceptor Photosensitizers
AU - Deckers, Jasper
AU - Cardeynaels, Tom
AU - Lutsen, Laurence
AU - Champagne, Benoît
AU - Maes, Wouter
N1 - Funding Information:
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).
Funding Information:
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).
Publisher Copyright:
© 2021 Wiley-VCH GmbH.
PY - 2021/7/16
Y1 - 2021/7/16
N2 - 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.
AB - 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.
KW - charge transfer
KW - intersystem crossing
KW - perylene diimides
KW - photosensitizers
KW - singlet oxygen
UR - http://www.scopus.com/inward/record.url?scp=85107894713&partnerID=8YFLogxK
U2 - 10.1002/cphc.202100269
DO - 10.1002/cphc.202100269
M3 - Article
C2 - 34031956
AN - SCOPUS:85107894713
SN - 1439-4235
VL - 22
SP - 1488
EP - 1496
JO - ChemPhysChem
JF - ChemPhysChem
IS - 14
ER -