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

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

doi:10.1002/cphc.202100269

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

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

Unit of theoretical and structural physico-chemistry

Research output: Contribution to journal › Article › peer-review

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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 language	English
Pages (from-to)	1488-1496
Number of pages	9
Journal	ChemPhysChem
Volume	22
Issue number	14
Early online date	25 May 2021
DOIs	https://doi.org/10.1002/cphc.202100269
Publication status	Published - 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

Access to Document

10.1002/cphc.202100269

ChemPhysChem 22 1488-1496 (2021)

Cite this

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title = "Heavy-Atom-Free Bay-Substituted Perylene Diimide Donor-Acceptor Photosensitizers",

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{\textquoteright}]dithiophene, 9,9-dimethyl-9,10-dihydroacridine, dithieno[3,2-b : 2{\textquoteright},3{\textquoteright}-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.",

keywords = "charge transfer, intersystem crossing, perylene diimides, photosensitizers, singlet oxygen",

author = "Jasper Deckers and Tom Cardeynaels and Laurence Lutsen and Beno{\^i}t Champagne and Wouter Maes",

note = "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) {\textquoteleft}Supramolecular Chemistry and Materials{\textquoteright} (W000620N). The calculations were performed on the computers of the {\textquoteleft}Consortium des {\'e}quipements de Calcul Intensif (C{\'E}CI){\textquoteright} ( http://www.ceci‐hpc.be ), including those of the {\textquoteleft}UNamur Technological Platform of High‐Performance Computing (PTCI){\textquoteright} ( 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: {\textcopyright} 2021 Wiley-VCH GmbH.",

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doi = "10.1002/cphc.202100269",

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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.

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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.

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KW - perylene diimides

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

Abstract

Funding

Keywords

Access to Document

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Fingerprint

Convention de collaboration/co-financement avec UHasselt

CÉCI – Consortium of high performance computing centers

High Performance Computing Technology Platform

Cite this

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

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Projects

Convention de collaboration/co-financement avec UHasselt

CÉCI – Consortium of high performance computing centers

Equipment

High Performance Computing Technology Platform

Cite this