Investigation of intramolecular through-space charge-transfer states in donor-acceptor charge-transfer systems

Shiv Kumar; Larissa Gomes Franca; Kleitos Stavrou; Ettore Crovini; David Bradford Cordes; Alexandra Martha Zoya Slawin; Andrew P. Monkman; Eli Zysman-Colman

doi:10.1021/acs.jpclett.1c00265

Investigation of intramolecular through-space charge-transfer states in donor-acceptor charge-transfer systems

Shiv Kumar, Larissa Gomes Franca, Kleitos Stavrou, Ettore Crovini, David Bradford Cordes, Alexandra Martha Zoya Slawin, Andrew P. Monkman, Eli Zysman-Colman

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

Abstract

Commonly, thermally activated delayed fluorescence (TADF) emitters present a twisted donor–acceptor structure. Here, electronic communication is mediated through-bond via π-conjugation between donor and acceptor groups. A second class of TADF emitters are those where electronic communication between donor and acceptor moieties is mediated through-space. In these through-space charge-transfer (TSCT) architectures, the donor and acceptor groups are disposed in a pseudocofacial orientation and linked via a bridging group that is typically an arene (or heteroarene). In most of these systems, there is no direct evidence that the TSCT is the dominant contributor to the communication between the donor and acceptor. Herein we investigate the interplay between through-bond localized excited (LE) and charge-transfer (CT) states and the TSCT in a rationally designed emitter, TPA-ace-TRZ, and a family of model compounds. From our photophysical studies, TSCT TADF in TPA-ace-TRZ is unambiguously confirmed and supported by theoretical modeling.

Original language	English
Pages (from-to)	2820-2830
Number of pages	11
Journal	Journal of Physical Chemistry Letters
Volume	12
Early online date	15 Mar 2021
DOIs	https://doi.org/10.1021/acs.jpclett.1c00265
Publication status	E-pub ahead of print - 15 Mar 2021

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Kumar_2021_JPCL_TSCT_CC
Copyright © 2021 The Authors. Published by American Chemical Society. ACS Author Choice. Open Access, licensed under a CC BY Attribution licence (https://creativecommons.org/licenses/by/4.0/).
Final published version, 3.9 MBLicence: CC BY

H2020 - ITN ELI ZYSMAN-COLMAN: H2020 MSCA ITN TADFlife
Zysman-Colman, E. (PI)
European Commission
1/10/18 → 30/09/22
Project: Standard
THF-OLED: H2020 MSCA Fellowship 2016 THF-OLED
Zysman-Colman, E. (PI)
European Commission
1/05/17 → 31/10/19
Project: Fellowship

Investigation of Intramolecular Through-Space Charge-Transfer States in Donor-Acceptor ChargeTransfer Systems (dataset)
Kumar, S. (Creator), Franca, G. (Creator), Stavrou, K. (Creator), Crovini, E. (Creator), Cordes, D. B. (Creator), Slawin, A. M. Z. (Creator), Monkman, A. P. (Creator) & Zysman-Colman, E. (Creator), University of St Andrews, 22 Mar 2021
DOI: 10.17630/0ae146df-b0f9-4590-9e7e-c30191cc4461
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@article{c405f414b0c4426dbaa36c039e554e00,

title = "Investigation of intramolecular through-space charge-transfer states in donor-acceptor charge-transfer systems",

abstract = "Commonly, thermally activated delayed fluorescence (TADF) emitters present a twisted donor–acceptor structure. Here, electronic communication is mediated through-bond via π-conjugation between donor and acceptor groups. A second class of TADF emitters are those where electronic communication between donor and acceptor moieties is mediated through-space. In these through-space charge-transfer (TSCT) architectures, the donor and acceptor groups are disposed in a pseudocofacial orientation and linked via a bridging group that is typically an arene (or heteroarene). In most of these systems, there is no direct evidence that the TSCT is the dominant contributor to the communication between the donor and acceptor. Herein we investigate the interplay between through-bond localized excited (LE) and charge-transfer (CT) states and the TSCT in a rationally designed emitter, TPA-ace-TRZ, and a family of model compounds. From our photophysical studies, TSCT TADF in TPA-ace-TRZ is unambiguously confirmed and supported by theoretical modeling.",

author = "Shiv Kumar and Franca, {Larissa Gomes} and Kleitos Stavrou and Ettore Crovini and Cordes, {David Bradford} and Slawin, {Alexandra Martha Zoya} and Monkman, {Andrew P.} and Eli Zysman-Colman",

note = "Funding: We thank EU horizon 2020 Grant Agreement No. 812872 (TADFlife) for funding. SK acknowledges the financial support from European Union{\textquoteright}s Horizon 2020 research and innovation programme under Marie Sk{\l}odowska Curie Individual Fellowship (MCIF; Agreement No. 748430- THF-OLED). ",

year = "2021",

month = mar,

day = "15",

doi = "10.1021/acs.jpclett.1c00265",

language = "English",

volume = "12",

pages = "2820--2830",

journal = "Journal of Physical Chemistry Letters",

issn = "1948-7185",

publisher = "American Chemical Society (ACS)",

}

TY - JOUR

T1 - Investigation of intramolecular through-space charge-transfer states in donor-acceptor charge-transfer systems

AU - Kumar, Shiv

AU - Franca, Larissa Gomes

AU - Stavrou, Kleitos

AU - Crovini, Ettore

AU - Cordes, David Bradford

AU - Slawin, Alexandra Martha Zoya

AU - Monkman, Andrew P.

AU - Zysman-Colman, Eli

N1 - Funding: We thank EU horizon 2020 Grant Agreement No. 812872 (TADFlife) for funding. SK acknowledges the financial support from European Union’s Horizon 2020 research and innovation programme under Marie Skłodowska Curie Individual Fellowship (MCIF; Agreement No. 748430- THF-OLED).

PY - 2021/3/15

Y1 - 2021/3/15

N2 - Commonly, thermally activated delayed fluorescence (TADF) emitters present a twisted donor–acceptor structure. Here, electronic communication is mediated through-bond via π-conjugation between donor and acceptor groups. A second class of TADF emitters are those where electronic communication between donor and acceptor moieties is mediated through-space. In these through-space charge-transfer (TSCT) architectures, the donor and acceptor groups are disposed in a pseudocofacial orientation and linked via a bridging group that is typically an arene (or heteroarene). In most of these systems, there is no direct evidence that the TSCT is the dominant contributor to the communication between the donor and acceptor. Herein we investigate the interplay between through-bond localized excited (LE) and charge-transfer (CT) states and the TSCT in a rationally designed emitter, TPA-ace-TRZ, and a family of model compounds. From our photophysical studies, TSCT TADF in TPA-ace-TRZ is unambiguously confirmed and supported by theoretical modeling.

AB - Commonly, thermally activated delayed fluorescence (TADF) emitters present a twisted donor–acceptor structure. Here, electronic communication is mediated through-bond via π-conjugation between donor and acceptor groups. A second class of TADF emitters are those where electronic communication between donor and acceptor moieties is mediated through-space. In these through-space charge-transfer (TSCT) architectures, the donor and acceptor groups are disposed in a pseudocofacial orientation and linked via a bridging group that is typically an arene (or heteroarene). In most of these systems, there is no direct evidence that the TSCT is the dominant contributor to the communication between the donor and acceptor. Herein we investigate the interplay between through-bond localized excited (LE) and charge-transfer (CT) states and the TSCT in a rationally designed emitter, TPA-ace-TRZ, and a family of model compounds. From our photophysical studies, TSCT TADF in TPA-ace-TRZ is unambiguously confirmed and supported by theoretical modeling.

U2 - 10.1021/acs.jpclett.1c00265

DO - 10.1021/acs.jpclett.1c00265

M3 - Article

SN - 1948-7185

VL - 12

SP - 2820

EP - 2830

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

ER -

Investigation of intramolecular through-space charge-transfer states in donor-acceptor charge-transfer systems

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Projects

H2020 - ITN ELI ZYSMAN-COLMAN: H2020 MSCA ITN TADFlife

THF-OLED: H2020 MSCA Fellowship 2016 THF-OLED

Datasets

Investigation of Intramolecular Through-Space Charge-Transfer States in Donor-Acceptor ChargeTransfer Systems (dataset)

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