Using the mechanical bond to tune the performance of a thermally activated delayed fluorescence emitter
Using the mechanical bond to tune the performance of a thermally activated delayed fluorescence emitter
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.
DFT calculations, MD simulations, photophysics, rotaxane, thermally activated delayed fluorescence
12066-12073
Rajamalli, Pachaiyappan
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Rizzi, Federica
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Li, Wenbo
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Jinks, Michael A
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Kumar Gupta, Abhishek
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Laidlaw, Beth A.
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Samuel, Ifor D. W.
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Penfold, Thomas J.
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Goldup, Stephen
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Zysman-Coleman, Eli
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17 May 2021
Rajamalli, Pachaiyappan
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Rizzi, Federica
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Li, Wenbo
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Jinks, Michael A
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Kumar Gupta, Abhishek
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Laidlaw, Beth A.
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Samuel, Ifor D. W.
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Penfold, Thomas J.
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Goldup, Stephen
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Zysman-Coleman, Eli
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Rajamalli, Pachaiyappan, Rizzi, Federica, Li, Wenbo, Jinks, Michael A, Kumar Gupta, Abhishek, Laidlaw, Beth A., Samuel, Ifor D. W., Penfold, Thomas J., Goldup, Stephen and Zysman-Coleman, Eli
(2021)
Using the mechanical bond to tune the performance of a thermally activated delayed fluorescence emitter.
Angewandte Chemie International Edition, 60 (21), .
(doi:10.1002/anie.202101870).
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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anie.202101870
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Accepted/In Press date: 4 March 2021
e-pub ahead of print date: 5 March 2021
Published date: 17 May 2021
Additional Information:
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
Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.
Keywords:
DFT calculations, MD simulations, photophysics, rotaxane, thermally activated delayed fluorescence
Identifiers
Local EPrints ID: 448734
URI: http://eprints.soton.ac.uk/id/eprint/448734
ISSN: 1433-7851
PURE UUID: 4565f7a1-8af8-4547-8eb2-db02709f7a89
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Date deposited: 04 May 2021 16:38
Last modified: 16 Mar 2024 12:01
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Contributors
Author:
Pachaiyappan Rajamalli
Author:
Federica Rizzi
Author:
Wenbo Li
Author:
Michael A Jinks
Author:
Abhishek Kumar Gupta
Author:
Beth A. Laidlaw
Author:
Ifor D. W. Samuel
Author:
Thomas J. Penfold
Author:
Eli Zysman-Coleman
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