Thermally activated and aggregation-regulated excitonic coupling enable emissive high-lying triplet excitons

Tao Wang; Joydip De; Sen Wu; Abhishek Kumar Gupta; Eli Zysman-Colman

doi:10.1002/anie.202206681

Thermally activated and aggregation-regulated excitonic coupling enable emissive high-lying triplet excitons

Tao Wang, Joydip De, Sen Wu, Abhishek Kumar Gupta, Eli Zysman-Colman^*

^*Corresponding author for this work

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

Abstract

Room-temperature phosphorescence (RTP) originating from higher-lying triplet excitons remains a rather rarely documented occurrence for purely organic molecular systems. Here, we report two naphthalene-based RTP luminophores whose phosphorescence emission is enabled by radiative decay of high-lying triplet excitons. In contrast, upon cooling the dominant phosphorescence originates from the lowest-lying triplet excited state, which is manifested by a red-shifted emission. Photophysical and theoretical studies reveal that the unusual RTP results from thermally activated excitonic coupling between different conformations of the compounds. Aggregation-regulated excitonic coupling is observed when increasing the doping concentration of the emitters in poly(methylmethacrylate) (PMMA). Further, the RTP quantum efficiency improves more than 80-fold in 1,3-bis(N-carbazolyl)benzene (mCP) compared to that in PMMA. This design principle offers important insight into triplet excited state dynamics and has been exploited in afterglow-indicating temperature sensing.

Original language	English
Article number	e202206681
Number of pages	11
Journal	Angewandte Chemie International Edition
Volume	61
Issue number	33
Early online date	4 Jul 2022
DOIs	https://doi.org/10.1002/anie.202206681
Publication status	Published - 8 Aug 2022

Keywords

Excitonic coupling
Higher-lying triplet excitons
Host-guest system
Room-temperature phosphorescence

Access to Document

10.1002/anie.202206681Licence: CC BY

Wang-2022-Thermally-activated-and-agreegation-AngewandteChem-06681-CCBY
Copyright © 2022 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, 10.6 MBLicence: CC BY

TADF DLC OLEDs: MSCA-IF-2020. TADF-DLC-OLEDs: Development of highly efficient solution-processable blue organic light-emitting diodes based on liquid-crystalline thermally activated delayed fluorescent emitter materials
Zysman-Colman, E. (PI)
European Commission
30/08/21 → 29/08/23
Project: Standard
Eli Zysman-colman SRF: New Frontiers in Multi-Resonance Thermally Activated Delayed Fluorescence Emitter Design for Organic Light-Emitting Diodes
Zysman-Colman, E. (PI)
The Royal Society
18/01/21 → 18/03/22
Project: Fellowship
TADF Emitters for OLEDs - Eli Zysman: TADF Emitters for OLEDs
Zysman-Colman, E. (PI)
EPSRC
1/03/17 → 31/03/21
Project: Standard

Thermally activated and aggregation-regulated excitonic coupling enable (dataset)
Wang, T. (Creator), De, J. (Creator), Wu, S. (Creator), Gupta, A. K. (Creator) & Zysman-Colman, E. (Creator), University of St Andrews, 25 Jul 2022
DOI: 10.17630/ffdb5242-9f36-4f68-b782-8ae240ab3896
Dataset

File

Cite this

@article{5ff6b68d2e8c43b8893e3a80fd586143,

title = "Thermally activated and aggregation-regulated excitonic coupling enable emissive high-lying triplet excitons",

abstract = "Room-temperature phosphorescence (RTP) originating from higher-lying triplet excitons remains a rather rarely documented occurrence for purely organic molecular systems. Here, we report two naphthalene-based RTP luminophores whose phosphorescence emission is enabled by radiative decay of high-lying triplet excitons. In contrast, upon cooling the dominant phosphorescence originates from the lowest-lying triplet excited state, which is manifested by a red-shifted emission. Photophysical and theoretical studies reveal that the unusual RTP results from thermally activated excitonic coupling between different conformations of the compounds. Aggregation-regulated excitonic coupling is observed when increasing the doping concentration of the emitters in poly(methylmethacrylate) (PMMA). Further, the RTP quantum efficiency improves more than 80-fold in 1,3-bis(N-carbazolyl)benzene (mCP) compared to that in PMMA. This design principle offers important insight into triplet excited state dynamics and has been exploited in afterglow-indicating temperature sensing.",

keywords = "Excitonic coupling, Higher-lying triplet excitons, Host-guest system, Room-temperature phosphorescence",

author = "Tao Wang and Joydip De and Sen Wu and Gupta, {Abhishek Kumar} and Eli Zysman-Colman",

note = "Funding: Horizon 2020 Framework Programme (Grant Number(s): 897098; Grant recipient(s): Tao Wang, Eli Zysman-Colman); Horizon 2020 Framework Programme (Grant Number(s): 101025143; Grant recipient(s): Eli Zysman-Colman, Joydip De); Engineering and Physical Sciences Research Council (Grant Number(s): EP/P010482/1; Grant recipient(s): Eli Zysman-Colman); Royal Society (Grant Number(s): SRF\R1\201089; Grant recipient(s): Abhishek Kumar Gupta, Eli Zysman-Colman); China Scholarship Council (GrantNumber(s): 201906250199; Grant recipient(s): Sen Wu)",

year = "2022",

month = aug,

day = "8",

doi = "10.1002/anie.202206681",

language = "English",

volume = "61",

journal = "Angewandte Chemie International Edition",

issn = "1433-7851",

publisher = "John Wiley & Sons, Ltd",

number = "33",

}

TY - JOUR

T1 - Thermally activated and aggregation-regulated excitonic coupling enable emissive high-lying triplet excitons

AU - Wang, Tao

AU - De, Joydip

AU - Wu, Sen

AU - Gupta, Abhishek Kumar

AU - Zysman-Colman, Eli

N1 - Funding: Horizon 2020 Framework Programme (Grant Number(s): 897098; Grant recipient(s): Tao Wang, Eli Zysman-Colman); Horizon 2020 Framework Programme (Grant Number(s): 101025143; Grant recipient(s): Eli Zysman-Colman, Joydip De); Engineering and Physical Sciences Research Council (Grant Number(s): EP/P010482/1; Grant recipient(s): Eli Zysman-Colman); Royal Society (Grant Number(s): SRF\R1\201089; Grant recipient(s): Abhishek Kumar Gupta, Eli Zysman-Colman); China Scholarship Council (GrantNumber(s): 201906250199; Grant recipient(s): Sen Wu)

PY - 2022/8/8

Y1 - 2022/8/8

N2 - Room-temperature phosphorescence (RTP) originating from higher-lying triplet excitons remains a rather rarely documented occurrence for purely organic molecular systems. Here, we report two naphthalene-based RTP luminophores whose phosphorescence emission is enabled by radiative decay of high-lying triplet excitons. In contrast, upon cooling the dominant phosphorescence originates from the lowest-lying triplet excited state, which is manifested by a red-shifted emission. Photophysical and theoretical studies reveal that the unusual RTP results from thermally activated excitonic coupling between different conformations of the compounds. Aggregation-regulated excitonic coupling is observed when increasing the doping concentration of the emitters in poly(methylmethacrylate) (PMMA). Further, the RTP quantum efficiency improves more than 80-fold in 1,3-bis(N-carbazolyl)benzene (mCP) compared to that in PMMA. This design principle offers important insight into triplet excited state dynamics and has been exploited in afterglow-indicating temperature sensing.

AB - Room-temperature phosphorescence (RTP) originating from higher-lying triplet excitons remains a rather rarely documented occurrence for purely organic molecular systems. Here, we report two naphthalene-based RTP luminophores whose phosphorescence emission is enabled by radiative decay of high-lying triplet excitons. In contrast, upon cooling the dominant phosphorescence originates from the lowest-lying triplet excited state, which is manifested by a red-shifted emission. Photophysical and theoretical studies reveal that the unusual RTP results from thermally activated excitonic coupling between different conformations of the compounds. Aggregation-regulated excitonic coupling is observed when increasing the doping concentration of the emitters in poly(methylmethacrylate) (PMMA). Further, the RTP quantum efficiency improves more than 80-fold in 1,3-bis(N-carbazolyl)benzene (mCP) compared to that in PMMA. This design principle offers important insight into triplet excited state dynamics and has been exploited in afterglow-indicating temperature sensing.

KW - Excitonic coupling

KW - Higher-lying triplet excitons

KW - Host-guest system

KW - Room-temperature phosphorescence

U2 - 10.1002/anie.202206681

DO - 10.1002/anie.202206681

M3 - Article

SN - 1433-7851

VL - 61

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 33

M1 - e202206681

ER -

Thermally activated and aggregation-regulated excitonic coupling enable emissive high-lying triplet excitons

Abstract

Keywords

Access to Document

Fingerprint

Projects

TADF DLC OLEDs: MSCA-IF-2020. TADF-DLC-OLEDs: Development of highly efficient solution-processable blue organic light-emitting diodes based on liquid-crystalline thermally activated delayed fluorescent emitter materials

Eli Zysman-colman SRF: New Frontiers in Multi-Resonance Thermally Activated Delayed Fluorescence Emitter Design for Organic Light-Emitting Diodes

TADF Emitters for OLEDs - Eli Zysman: TADF Emitters for OLEDs

Datasets

Thermally activated and aggregation-regulated excitonic coupling enable (dataset)

Cite this