Oxidation State Tuning of Room Temperature Phosphorescence and Delayed Fluorescence in Phenothiazine and Phenothiazine‐5,5‐dioxide Dimers

Iain A. Wright; Marc K. Etherington; Andrei S. Batsanov; Andrew P. Monkman; Martin R. Bryce

doi:10.1002/chem.202300428

Oxidation State Tuning of Room Temperature Phosphorescence and Delayed Fluorescence in Phenothiazine and Phenothiazine‐5,5‐dioxide Dimers

Iain A. Wright^*, Marc K. Etherington, Andrei S. Batsanov, Andrew P. Monkman, Martin R. Bryce

^*Corresponding author for this work

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

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Abstract

Heterocyclic dimers consisting of combinations of butterfly-shaped phenothiazine (PTZ) and its chemically oxidized form phenothiazine-5,5-dioxide (PTZSO2) have been synthesized. A twist is imposed across the dimers by ortho-substituents including methyl ethers, sulfides and sulfones. X-ray crystallography, cyclic voltammetry and optical spectroscopy, underpinned by computational studies, have been employed to study the interplay between the oxidation state, conformational restriction, and emission mechanisms including thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP). While the PTZSO2 dimers are simple fluorophores, the presence of PTZ induces triplet-mediated emission with a mixed PTZ-PTZSO2 dimer displaying concentration dependent hallmarks of both TADF and RTP.

Original language	English
Article number	e202300428
Pages (from-to)	1-11
Number of pages	11
Journal	Chemistry - A European Journal
Volume	29
Issue number	30
Early online date	19 Apr 2023
DOIs	https://doi.org/10.1002/chem.202300428
Publication status	Published - 26 May 2023

Keywords

delayed fluorescence
heterocycles
oxidation
phenothiazine
photophysics

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10.1002/chem.202300428Licence: CC BY

Chemistry A European J - 2023 - Wright - Oxidation State Tuning of Room Temperature Phosphorescence and DelayedAccepted author manuscript, 2.66 MBLicence: CC BY
Chemistry A European J - 2023 - Wright - Oxidation State Tuning of Room Temperature Phosphorescence and DelayedFinal published version, 3.42 MBLicence: CC BY

Cite this

@article{156951cbcd6948578b974c82bfb15812,

title = "Oxidation State Tuning of Room Temperature Phosphorescence and Delayed Fluorescence in Phenothiazine and Phenothiazine‐5,5‐dioxide Dimers",

abstract = "Heterocyclic dimers consisting of combinations of butterfly-shaped phenothiazine (PTZ) and its chemically oxidized form phenothiazine-5,5-dioxide (PTZSO2) have been synthesized. A twist is imposed across the dimers by ortho-substituents including methyl ethers, sulfides and sulfones. X-ray crystallography, cyclic voltammetry and optical spectroscopy, underpinned by computational studies, have been employed to study the interplay between the oxidation state, conformational restriction, and emission mechanisms including thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP). While the PTZSO2 dimers are simple fluorophores, the presence of PTZ induces triplet-mediated emission with a mixed PTZ-PTZSO2 dimer displaying concentration dependent hallmarks of both TADF and RTP.",

keywords = "delayed fluorescence, heterocycles, oxidation, phenothiazine, photophysics",

author = "Wright, \{Iain A.\} and Etherington, \{Marc K.\} and Batsanov, \{Andrei S.\} and Monkman, \{Andrew P.\} and Bryce, \{Martin R.\}",

note = "Funding information: The authors acknowledge the financial support of EPSRC grant EP/K016164/1. IAW acknowledges financial support from the RSC Research Fund grant number RF19-2751 and EPSRC grant EP/T028688/1. APM and MRB were supported by the HyperOLED project from the European Union{\textquoteright}s Horizon 2020 research and innovation program under grant agreement number 732013.",

year = "2023",

month = may,

day = "26",

doi = "10.1002/chem.202300428",

language = "English",

volume = "29",

pages = "1--11",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Blackwell Publishing",

number = "30",

}

TY - JOUR

T1 - Oxidation State Tuning of Room Temperature Phosphorescence and Delayed Fluorescence in Phenothiazine and Phenothiazine‐5,5‐dioxide Dimers

AU - Wright, Iain A.

AU - Etherington, Marc K.

AU - Batsanov, Andrei S.

AU - Monkman, Andrew P.

AU - Bryce, Martin R.

N1 - Funding information: The authors acknowledge the financial support of EPSRC grant EP/K016164/1. IAW acknowledges financial support from the RSC Research Fund grant number RF19-2751 and EPSRC grant EP/T028688/1. APM and MRB were supported by the HyperOLED project from the European Union’s Horizon 2020 research and innovation program under grant agreement number 732013.

PY - 2023/5/26

Y1 - 2023/5/26

N2 - Heterocyclic dimers consisting of combinations of butterfly-shaped phenothiazine (PTZ) and its chemically oxidized form phenothiazine-5,5-dioxide (PTZSO2) have been synthesized. A twist is imposed across the dimers by ortho-substituents including methyl ethers, sulfides and sulfones. X-ray crystallography, cyclic voltammetry and optical spectroscopy, underpinned by computational studies, have been employed to study the interplay between the oxidation state, conformational restriction, and emission mechanisms including thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP). While the PTZSO2 dimers are simple fluorophores, the presence of PTZ induces triplet-mediated emission with a mixed PTZ-PTZSO2 dimer displaying concentration dependent hallmarks of both TADF and RTP.

AB - Heterocyclic dimers consisting of combinations of butterfly-shaped phenothiazine (PTZ) and its chemically oxidized form phenothiazine-5,5-dioxide (PTZSO2) have been synthesized. A twist is imposed across the dimers by ortho-substituents including methyl ethers, sulfides and sulfones. X-ray crystallography, cyclic voltammetry and optical spectroscopy, underpinned by computational studies, have been employed to study the interplay between the oxidation state, conformational restriction, and emission mechanisms including thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP). While the PTZSO2 dimers are simple fluorophores, the presence of PTZ induces triplet-mediated emission with a mixed PTZ-PTZSO2 dimer displaying concentration dependent hallmarks of both TADF and RTP.

KW - delayed fluorescence

KW - heterocycles

KW - oxidation

KW - phenothiazine

KW - photophysics

UR - https://www.scopus.com/pages/publications/85152936665

U2 - 10.1002/chem.202300428

DO - 10.1002/chem.202300428

M3 - Article

SN - 0947-6539

VL - 29

SP - 1

EP - 11

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 30

M1 - e202300428

ER -

Oxidation State Tuning of Room Temperature Phosphorescence and Delayed Fluorescence in Phenothiazine and Phenothiazine‐5,5‐dioxide Dimers

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