Computationally Guided Molecular Design to Minimize the LE/CT Gap in D-π-A Fluorinated Triarylboranes for Efficient TADF via D and π-Bridge Tuning

Ayush K. Narsaria; Florian Rauch; Johannes Krebs; Peter Endres; Alexandra Friedrich; Ivo Krummenacher; Holger Braunschweig; Maik Finze; Jörn Nitsch; F. Matthias Bickelhaupt; Todd B. Marder

doi:10.1002/adfm.202002064

Computationally Guided Molecular Design to Minimize the LE/CT Gap in D-π-A Fluorinated Triarylboranes for Efficient TADF via D and π-Bridge Tuning

Ayush K. Narsaria, Florian Rauch, Johannes Krebs, Peter Endres, Alexandra Friedrich, Ivo Krummenacher, Holger Braunschweig, Maik Finze, Jörn Nitsch, F. Matthias Bickelhaupt^*, Todd B. Marder

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

In this combined experimental and theoretical study, a computational protocol is reported to predict the excited states in D-π-A compounds containing the B(^FXyl)₂ (^FXyl = 2,6-bis(trifluoromethyl)phenyl) acceptor group for the design of new thermally activated delayed fluorescence (TADF) emitters. To this end, the effect of different donor and π-bridge moieties on the energy gaps between local and charge-transfer singlet and triplet states is examined. To prove this computationally aided design concept, the D-π-B(^FXyl)₂ compounds 1–5 were synthesized and fully characterized. The photophysical properties of these compounds in various solvents, polymeric film, and in a frozen matrix were investigated in detail and show excellent agreement with the computationally obtained data. Furthermore, a simple structure–property relationship is presented on the basis of the molecular fragment orbitals of the donor and the π-bridge, which minimize the relevant singlet–triplet gaps to achieve efficient TADF emitters.

Original language	English
Article number	2002064
Pages (from-to)	1-15
Number of pages	15
Journal	Advanced Functional Materials
Volume	30
Issue number	31
Early online date	2 Jun 2020
DOIs	https://doi.org/10.1002/adfm.202002064
Publication status	Published - 1 Aug 2020

Funding

A.K.N. and F.R. contributed equally to this work. Financial support from the Julius-Maximilians-Universit?t W?rzburg and the Netherlands Organisation for Scientific Research (NWO) is gratefully acknowledged. T.B.M. thanks the Bavarian State Ministry of Science, Research, and the Arts for the Collaborative Research Network ?Solar Technologies go Hybrid? for funding. F.M.B. thanks the Industrial Partnership Program (IPP) ?Computational Sciences for Energy Research? (project 14CSER011) which is part of the Netherlands Organization for Scientific Research (NWO) and is co-financed by Shell Global Solutions International B.V. J.N. thanks the Deutsche Forschungsgemeinschaft for a Research Fellowship (NI 1737/1-1) and a DFG Return Fellowship (NI 1737/2-1). A.K.N. thanks Erik van Lenthe for stimulating discussions on modeling the energy gaps. B2pin2 was kindly donated by AllyChem Co. Ltd. (Dalian, China). All authors thank Verena Borawski for preparing the TOC.

Funders	Funder number
Verena Borawski
Shell Global Solutions International
Deutsche Forschungsgemeinschaft	NI 1737/1‐1, NI 1737/2‐1
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Bayerisches Staatsministerium für Wissenschaft, Forschung und Kunst	14CSER011
Julius-Maximilians-Universität Würzburg

Keywords

boron
charge transfer
delayed fluorescence
organic light-emitting diodes
singlet–triplet gap quantum efficiency

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/adfm.202002064

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Narsaria, A. K., Rauch, F., Krebs, J., Endres, P., Friedrich, A., Krummenacher, I., Braunschweig, H., Finze, M., Nitsch, J., Bickelhaupt, F. M., & Marder, T. B. (2020). Computationally Guided Molecular Design to Minimize the LE/CT Gap in D-π-A Fluorinated Triarylboranes for Efficient TADF via D and π-Bridge Tuning. Advanced Functional Materials, 30(31), 1-15. Article 2002064. https://doi.org/10.1002/adfm.202002064

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title = "Computationally Guided Molecular Design to Minimize the LE/CT Gap in D-π-A Fluorinated Triarylboranes for Efficient TADF via D and π-Bridge Tuning",

abstract = "In this combined experimental and theoretical study, a computational protocol is reported to predict the excited states in D-π-A compounds containing the B(FXyl)2 (FXyl = 2,6-bis(trifluoromethyl)phenyl) acceptor group for the design of new thermally activated delayed fluorescence (TADF) emitters. To this end, the effect of different donor and π-bridge moieties on the energy gaps between local and charge-transfer singlet and triplet states is examined. To prove this computationally aided design concept, the D-π-B(FXyl)2 compounds 1–5 were synthesized and fully characterized. The photophysical properties of these compounds in various solvents, polymeric film, and in a frozen matrix were investigated in detail and show excellent agreement with the computationally obtained data. Furthermore, a simple structure–property relationship is presented on the basis of the molecular fragment orbitals of the donor and the π-bridge, which minimize the relevant singlet–triplet gaps to achieve efficient TADF emitters.",

keywords = "boron, charge transfer, delayed fluorescence, organic light-emitting diodes, singlet–triplet gap quantum efficiency",

author = "Narsaria, {Ayush K.} and Florian Rauch and Johannes Krebs and Peter Endres and Alexandra Friedrich and Ivo Krummenacher and Holger Braunschweig and Maik Finze and J{\"o}rn Nitsch and Bickelhaupt, {F. Matthias} and Marder, {Todd B.}",

year = "2020",

month = aug,

day = "1",

doi = "10.1002/adfm.202002064",

language = "English",

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Narsaria, AK, Rauch, F, Krebs, J, Endres, P, Friedrich, A, Krummenacher, I, Braunschweig, H, Finze, M, Nitsch, J, Bickelhaupt, FM & Marder, TB 2020, 'Computationally Guided Molecular Design to Minimize the LE/CT Gap in D-π-A Fluorinated Triarylboranes for Efficient TADF via D and π-Bridge Tuning', Advanced Functional Materials, vol. 30, no. 31, 2002064, pp. 1-15. https://doi.org/10.1002/adfm.202002064

Computationally Guided Molecular Design to Minimize the LE/CT Gap in D-π-A Fluorinated Triarylboranes for Efficient TADF via D and π-Bridge Tuning. / Narsaria, Ayush K.; Rauch, Florian; Krebs, Johannes et al.
In: Advanced Functional Materials, Vol. 30, No. 31, 2002064, 01.08.2020, p. 1-15.

Research output: Contribution to Journal › Article › Academic › peer-review

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T1 - Computationally Guided Molecular Design to Minimize the LE/CT Gap in D-π-A Fluorinated Triarylboranes for Efficient TADF via D and π-Bridge Tuning

AU - Narsaria, Ayush K.

AU - Rauch, Florian

AU - Krebs, Johannes

AU - Endres, Peter

AU - Friedrich, Alexandra

AU - Krummenacher, Ivo

AU - Braunschweig, Holger

AU - Finze, Maik

AU - Nitsch, Jörn

AU - Bickelhaupt, F. Matthias

AU - Marder, Todd B.

PY - 2020/8/1

Y1 - 2020/8/1

N2 - In this combined experimental and theoretical study, a computational protocol is reported to predict the excited states in D-π-A compounds containing the B(FXyl)2 (FXyl = 2,6-bis(trifluoromethyl)phenyl) acceptor group for the design of new thermally activated delayed fluorescence (TADF) emitters. To this end, the effect of different donor and π-bridge moieties on the energy gaps between local and charge-transfer singlet and triplet states is examined. To prove this computationally aided design concept, the D-π-B(FXyl)2 compounds 1–5 were synthesized and fully characterized. The photophysical properties of these compounds in various solvents, polymeric film, and in a frozen matrix were investigated in detail and show excellent agreement with the computationally obtained data. Furthermore, a simple structure–property relationship is presented on the basis of the molecular fragment orbitals of the donor and the π-bridge, which minimize the relevant singlet–triplet gaps to achieve efficient TADF emitters.

AB - In this combined experimental and theoretical study, a computational protocol is reported to predict the excited states in D-π-A compounds containing the B(FXyl)2 (FXyl = 2,6-bis(trifluoromethyl)phenyl) acceptor group for the design of new thermally activated delayed fluorescence (TADF) emitters. To this end, the effect of different donor and π-bridge moieties on the energy gaps between local and charge-transfer singlet and triplet states is examined. To prove this computationally aided design concept, the D-π-B(FXyl)2 compounds 1–5 were synthesized and fully characterized. The photophysical properties of these compounds in various solvents, polymeric film, and in a frozen matrix were investigated in detail and show excellent agreement with the computationally obtained data. Furthermore, a simple structure–property relationship is presented on the basis of the molecular fragment orbitals of the donor and the π-bridge, which minimize the relevant singlet–triplet gaps to achieve efficient TADF emitters.

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KW - delayed fluorescence

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KW - singlet–triplet gap quantum efficiency

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M3 - Article

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SN - 1616-301X

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ER -

Computationally Guided Molecular Design to Minimize the LE/CT Gap in D-π-A Fluorinated Triarylboranes for Efficient TADF via D and π-Bridge Tuning

Abstract

Funding

Keywords

UN SDGs

Access to Document

Persistent URL (handle)

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CCDC 1949270: Experimental Crystal Structure Determination

CCDC 1949274: Experimental Crystal Structure Determination

CCDC 1949276: Experimental Crystal Structure Determination

Cite this

Computationally Guided Molecular Design to Minimize the LE/CT Gap in D-π-A Fluorinated Triarylboranes for Efficient TADF via D and π-Bridge Tuning

Abstract

Funding

Keywords

UN SDGs

Access to Document

Persistent URL (handle)

Other files and links

Fingerprint

Datasets

CCDC 1949270: Experimental Crystal Structure Determination

CCDC 1949274: Experimental Crystal Structure Determination

CCDC 1949276: Experimental Crystal Structure Determination

Cite this