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 Laidlaw; Ifor David William 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 Laidlaw, Ifor David William Samuel^*, Thomas J. Penfold^*, Stephen M. Goldup^*, Eli Zysman-Colman^*

^*Corresponding author for this work

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

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 - 11 May 2021

Keywords

Luminescence
Mechanical bond
Rotaxane
Supramolecular chemistry
TADF

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Rajamalli_2021_ACie_Using-mechanical_CC
Copyright © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 1.63 MBLicence: CC BY

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.",

keywords = "Luminescence, Mechanical bond, Rotaxane, Supramolecular chemistry, TADF",

author = "Pachaiyappan Rajamalli and Federica Rizzi and Wenbo Li and Jinks, {Michael A.} and Gupta, {Abhishek Kumar} and Beth Laidlaw and Samuel, {Ifor David William} and Penfold, {Thomas J.} and Goldup, {Stephen M.} and Eli Zysman-Colman",

note = "Funding: P.R. acknowledges support from a Marie Sk{\l}odowska-Curie Individual Fellowship (MCIF; No. 749557). EZ-C thanks the Leverhulme trust for support (RPG-2016-047). T.J.P acknowledges the EPSRC (EP/P012388/1, EP/T022442/1) for support. EZ-C and IDWS 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). ",

year = "2021",

month = may,

day = "11",

doi = "10.1002/anie.202101870",

language = "English",

volume = "60",

pages = "12066--12073",

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publisher = "John Wiley & Sons, Ltd",

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TY - JOUR

T1 - Using the mechanical bond to tune the performance of a thermally activated delayed fluorescence emitter

AU - Rajamalli, Pachaiyappan

AU - Rizzi, Federica

AU - Li, Wenbo

AU - Jinks, Michael A.

AU - Gupta, Abhishek Kumar

AU - Laidlaw, Beth

AU - Samuel, Ifor David William

AU - Penfold, Thomas J.

AU - Goldup, Stephen M.

AU - Zysman-Colman, Eli

N1 - Funding: P.R. acknowledges support from a Marie Skłodowska-Curie Individual Fellowship (MCIF; No. 749557). EZ-C thanks the Leverhulme trust for support (RPG-2016-047). T.J.P acknowledges the EPSRC (EP/P012388/1, EP/T022442/1) for support. EZ-C and IDWS 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).

PY - 2021/5/11

Y1 - 2021/5/11

N2 - 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.

AB - 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.

KW - Luminescence

KW - Mechanical bond

KW - Rotaxane

KW - Supramolecular chemistry

KW - TADF

UR - https://doi.org/10.26434/chemrxiv.13696483.v1

U2 - 10.1002/anie.202101870

DO - 10.1002/anie.202101870

M3 - Article

SN - 1433-7851

VL - 60

SP - 12066

EP - 12073

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 21

ER -

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

Abstract

Keywords

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CCDC 2061107: Experimental Crystal Structure Determination