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 - http://www.scopus.com/inward/record.url?scp=85152936665&partnerID=8YFLogxK
U2 - 10.1002/chem.202300428
DO - 10.1002/chem.202300428
M3 - Article
VL - 29
SP - 1
EP - 11
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 30
M1 - e202300428
ER -