Using the mechanical bond to tune the performance of a thermally activated delayed fluorescence emitter**

Pachaiyappan Rajamalli; Federica Rizzi; Wenbo Li; Michael A. Jinks; Abhishek Kumar Gupta; Beth A. Laidlaw; Ifor D.W. Samuel; Thomas J. Penfold; Stephen M. Goldup; Eli Zysman-Colman

doi:10.1002/anie.202101870

Using the mechanical bond to tune the performance of a thermally activated delayed fluorescence emitter**

Pachaiyappan Rajamalli, Federica Rizzi, Wenbo Li, Michael A. Jinks, Abhishek Kumar Gupta, Beth A. Laidlaw, Ifor D.W. Samuel^*, Thomas J. Penfold^*, Stephen M. Goldup^*, Eli Zysman-Colman^*

^*Corresponding author for this work

Chemistry

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

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Abstract

We report the characterization of rotaxanes based on a carbazole-benzophenone thermally activated delayed fluorescence luminophore. We find that the mechanical bond leads to an improvement in key photophysical properties of the emitter, notably an increase in photoluminescence quantum yield and a decrease in the energy difference between singlet and triplet states, as well as fine tuning of the emission wavelength, a feat that is difficult to achieve when using covalently bound substituents. Computational simulations, supported by X-ray crystallography, suggest that this tuning of properties occurs due to weak interactions between the axle and the macrocycle that are enforced by the mechanical bond. This work highlights the benefits of using the mechanical bond to refine existing luminophores, providing a new avenue for emitter optimization that can ultimately increase the performance of these molecules.

Original language	English
Pages (from-to)	12066-12073
Number of pages	8
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	21
Early online date	5 Mar 2021
DOIs	https://doi.org/10.1002/anie.202101870
Publication status	Published - 17 May 2021

Bibliographical note

Funding Information:
P.R. acknowledges support from a Marie Skłodowska‐Curie Individual Fellowship (MCIF; No. 749557). E.Z.‐C. thanks the Leverhulme trust for support (RPG‐2016‐047). T.J.P. acknowledges the EPSRC (EP/P012388/1, EP/T022442/1) for support. E.Z.‐C. and I.D.W..S acknowledge support from EPSRC (EP/L017008, EP/P010482/1). SMG thanks the European Research Council (Consolidator Grant Agreement no. 724987) and the Leverhulme Trust (ORPG‐2733) for funding and the Royal Society for a Wolfson Research Fellowship. W.L. acknowledges support from China Scholarship Council (201708060003). The authors thank Drs Peter Horton and Graham Tizzard of the National Crystallographic Service for assistance with X‐ray diffraction analysis. A.K.G. is thankful to the Royal Society for Newton International Fellowship NF171163. We are also grateful for financial support from the University of St Andrews Restarting Research Funding Scheme (SARRF), which is funded through the Scottish Funding Council grant reference SFC/AN/08/020.

Publisher Copyright:
© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

Keywords

luminescence
mechanical bond
rotaxane
supramolecular chemistry
TADF

ASJC Scopus subject areas

Catalysis
General Chemistry

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Cite this

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title = "Using the mechanical bond to tune the performance of a thermally activated delayed fluorescence emitter**",

abstract = "We report the characterization of rotaxanes based on a carbazole-benzophenone thermally activated delayed fluorescence luminophore. We find that the mechanical bond leads to an improvement in key photophysical properties of the emitter, notably an increase in photoluminescence quantum yield and a decrease in the energy difference between singlet and triplet states, as well as fine tuning of the emission wavelength, a feat that is difficult to achieve when using covalently bound substituents. Computational simulations, supported by X-ray crystallography, suggest that this tuning of properties occurs due to weak interactions between the axle and the macrocycle that are enforced by the mechanical bond. This work highlights the benefits of using the mechanical bond to refine existing luminophores, providing a new avenue for emitter optimization that can ultimately increase the performance of these molecules.",

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note = "Funding Information: P.R. acknowledges support from a Marie Sk{\l}odowska‐Curie Individual Fellowship (MCIF; No. 749557). E.Z.‐C. thanks the Leverhulme trust for support (RPG‐2016‐047). T.J.P. acknowledges the EPSRC (EP/P012388/1, EP/T022442/1) for support. E.Z.‐C. and I.D.W..S acknowledge support from EPSRC (EP/L017008, EP/P010482/1). SMG thanks the European Research Council (Consolidator Grant Agreement no. 724987) and the Leverhulme Trust (ORPG‐2733) for funding and the Royal Society for a Wolfson Research Fellowship. W.L. acknowledges support from China Scholarship Council (201708060003). The authors thank Drs Peter Horton and Graham Tizzard of the National Crystallographic Service for assistance with X‐ray diffraction analysis. A.K.G. is thankful to the Royal Society for Newton International Fellowship NF171163. We are also grateful for financial support from the University of St Andrews Restarting Research Funding Scheme (SARRF), which is funded through the Scottish Funding Council grant reference SFC/AN/08/020. Publisher Copyright: {\textcopyright} 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH",

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AU - Penfold, Thomas J.

AU - Goldup, Stephen M.

AU - Zysman-Colman, Eli

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Using the mechanical bond to tune the performance of a thermally activated delayed fluorescence emitter**

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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