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Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters

Alexander J. Gillett Orcid Logo, Anton Pershin Orcid Logo, Raj Pandya, Sascha Feldmann Orcid Logo, Alexander J. Sneyd Orcid Logo, Antonios M. Alvertis, Emrys Evans Orcid Logo, Tudor H. Thomas, Lin-Song Cui Orcid Logo, Bluebell H. Drummond Orcid Logo, Gregory D. Scholes Orcid Logo, Yoann Olivier, Akshay Rao Orcid Logo, Richard H. Friend Orcid Logo, David Beljonne Orcid Logo

Nature Materials, Volume: 21, Issue: 10, Pages: 1150 - 1157

Swansea University Author: Emrys Evans Orcid Logo

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DOI (Published version): 10.1038/s41563-022-01321-2

Abstract

Thermally activated delayed fluorescence enables organic semiconductors with charge transfer-type excitons to convert dark triplet states into bright singlets via reverse intersystem crossing. However, thus far, the contribution from the dielectric environment has received insufficient attention. He...

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Published in: Nature Materials
ISSN: 1476-1122 1476-4660
Published: Springer Science and Business Media LLC 2022
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URI: https://cronfa.swan.ac.uk/Record/cronfa60976
first_indexed 2022-09-14T14:02:11Z
last_indexed 2023-01-13T19:21:30Z
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Here we study the role of the dielectric environment in a range of thermally activated delayed fluorescence materials with varying changes in dipole moment upon optical excitation. In dipolar emitters, we observe how environmental reorganization after excitation triggers the full charge transfer exciton formation, minimizing the singlet&#x2013;triplet energy gap, with the emergence of two (reactant-inactive) modes acting as a vibrational fingerprint of the charge transfer product. In contrast, the dielectric environment plays a smaller role in less dipolar materials. The analysis of energy&#x2013;time trajectories and their free-energy functions reveals that the dielectric environment substantially reduces the activation energy for reverse intersystem crossing in dipolar thermally activated delayed fluorescence emitters, increasing the reverse intersystem crossing rate by three orders of magnitude versus the isolated molecule.</abstract><type>Journal Article</type><journal>Nature Materials</journal><volume>21</volume><journalNumber>10</journalNumber><paginationStart>1150</paginationStart><paginationEnd>1157</paginationEnd><publisher>Springer Science and Business Media LLC</publisher><placeOfPublication/><isbnPrint/><isbnElectronic/><issnPrint>1476-1122</issnPrint><issnElectronic>1476-4660</issnElectronic><keywords>Atomistic models, Molecular dynamics, Organic LEDs, Optical spectroscopy</keywords><publishedDay>1</publishedDay><publishedMonth>10</publishedMonth><publishedYear>2022</publishedYear><publishedDate>2022-10-01</publishedDate><doi>10.1038/s41563-022-01321-2</doi><url/><notes/><college>COLLEGE NANME</college><department>Engineering and Applied Sciences School</department><CollegeCode>COLLEGE CODE</CollegeCode><DepartmentCode>EAAS</DepartmentCode><institution>Swansea University</institution><apcterm/><funders>A.J.G. and R.H.F. acknowledge support from the Simons Foundation (grant no. 601946) and the Engineering and Physical Sciences Research Council (EPSRC) (EP/M01083X/1 and EP/M005143/1). This project has received funding from the European Research Council under the European Union&#x2019;s Horizon 2020 research and innovation programme (R.H.F., grant agreement no. 670405; A.R., grant agreement no. 758826). A.R. thanks the Winton Programme for the Physics of Sustainability for funding. A.P., Y.O. and D.B. were supported by the European Union&#x2019;s Horizon 2020 research and innovation programme under Marie Sklodowska Curie Grant agreement 748042 (MILORD project). R.P. acknowledges financial support from an EPSRC Doctoral Prize Fellowship. A.J.S. acknowledges the Royal Society Te Ap&#x101;rangi and the Cambridge Commonwealth European and International Trust for their financial support. Y.O. acknowledges funding by the FNRS under grant no. F.4534.21 (MIS-IMAGINE). 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spelling 2022-11-20T10:46:14.6503082 v2 60976 2022-08-30 Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters 538e217307dac24c9642ef1b03b41485 0000-0002-9092-3938 Emrys Evans Emrys Evans true false 2022-08-30 EAAS Thermally activated delayed fluorescence enables organic semiconductors with charge transfer-type excitons to convert dark triplet states into bright singlets via reverse intersystem crossing. However, thus far, the contribution from the dielectric environment has received insufficient attention. Here we study the role of the dielectric environment in a range of thermally activated delayed fluorescence materials with varying changes in dipole moment upon optical excitation. In dipolar emitters, we observe how environmental reorganization after excitation triggers the full charge transfer exciton formation, minimizing the singlet–triplet energy gap, with the emergence of two (reactant-inactive) modes acting as a vibrational fingerprint of the charge transfer product. In contrast, the dielectric environment plays a smaller role in less dipolar materials. The analysis of energy–time trajectories and their free-energy functions reveals that the dielectric environment substantially reduces the activation energy for reverse intersystem crossing in dipolar thermally activated delayed fluorescence emitters, increasing the reverse intersystem crossing rate by three orders of magnitude versus the isolated molecule. Journal Article Nature Materials 21 10 1150 1157 Springer Science and Business Media LLC 1476-1122 1476-4660 Atomistic models, Molecular dynamics, Organic LEDs, Optical spectroscopy 1 10 2022 2022-10-01 10.1038/s41563-022-01321-2 COLLEGE NANME Engineering and Applied Sciences School COLLEGE CODE EAAS Swansea University A.J.G. and R.H.F. acknowledge support from the Simons Foundation (grant no. 601946) and the Engineering and Physical Sciences Research Council (EPSRC) (EP/M01083X/1 and EP/M005143/1). This project has received funding from the European Research Council under the European Union’s Horizon 2020 research and innovation programme (R.H.F., grant agreement no. 670405; A.R., grant agreement no. 758826). A.R. thanks the Winton Programme for the Physics of Sustainability for funding. A.P., Y.O. and D.B. were supported by the European Union’s Horizon 2020 research and innovation programme under Marie Sklodowska Curie Grant agreement 748042 (MILORD project). R.P. acknowledges financial support from an EPSRC Doctoral Prize Fellowship. A.J.S. acknowledges the Royal Society Te Apārangi and the Cambridge Commonwealth European and International Trust for their financial support. Y.O. acknowledges funding by the FNRS under grant no. F.4534.21 (MIS-IMAGINE). L.-S.C. acknowledges funding from the University of Science and Technology of China (USTC) Research Funds of the Double First-Class Initiative and the National Natural Science Foundation of China (grant no. 52103242). 2022-11-20T10:46:14.6503082 2022-08-30T11:46:07.3023227 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Alexander J. Gillett 0000-0001-7572-7333 1 Anton Pershin 0000-0002-2414-6405 2 Raj Pandya 3 Sascha Feldmann 0000-0002-6583-5354 4 Alexander J. Sneyd 0000-0002-4205-0554 5 Antonios M. Alvertis 6 Emrys Evans 0000-0002-9092-3938 7 Tudor H. Thomas 8 Lin-Song Cui 0000-0001-6577-3432 9 Bluebell H. Drummond 0000-0001-5940-8631 10 Gregory D. Scholes 0000-0003-3336-7960 11 Yoann Olivier 12 Akshay Rao 0000-0003-4261-0766 13 Richard H. Friend 0000-0001-6565-6308 14 David Beljonne 0000-0001-5082-9990 15
title Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters
spellingShingle Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters
Emrys Evans
title_short Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters
title_full Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters
title_fullStr Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters
title_full_unstemmed Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters
title_sort Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters
author_id_str_mv 538e217307dac24c9642ef1b03b41485
author_id_fullname_str_mv 538e217307dac24c9642ef1b03b41485_***_Emrys Evans
author Emrys Evans
author2 Alexander J. Gillett
Anton Pershin
Raj Pandya
Sascha Feldmann
Alexander J. Sneyd
Antonios M. Alvertis
Emrys Evans
Tudor H. Thomas
Lin-Song Cui
Bluebell H. Drummond
Gregory D. Scholes
Yoann Olivier
Akshay Rao
Richard H. Friend
David Beljonne
format Journal article
container_title Nature Materials
container_volume 21
container_issue 10
container_start_page 1150
publishDate 2022
institution Swansea University
issn 1476-1122
1476-4660
doi_str_mv 10.1038/s41563-022-01321-2
publisher Springer Science and Business Media LLC
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemistry{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemistry
document_store_str 0
active_str 0
description Thermally activated delayed fluorescence enables organic semiconductors with charge transfer-type excitons to convert dark triplet states into bright singlets via reverse intersystem crossing. However, thus far, the contribution from the dielectric environment has received insufficient attention. Here we study the role of the dielectric environment in a range of thermally activated delayed fluorescence materials with varying changes in dipole moment upon optical excitation. In dipolar emitters, we observe how environmental reorganization after excitation triggers the full charge transfer exciton formation, minimizing the singlet–triplet energy gap, with the emergence of two (reactant-inactive) modes acting as a vibrational fingerprint of the charge transfer product. In contrast, the dielectric environment plays a smaller role in less dipolar materials. The analysis of energy–time trajectories and their free-energy functions reveals that the dielectric environment substantially reduces the activation energy for reverse intersystem crossing in dipolar thermally activated delayed fluorescence emitters, increasing the reverse intersystem crossing rate by three orders of magnitude versus the isolated molecule.
published_date 2022-10-01T20:27:07Z
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score 11.047609

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