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Synthesis and Exciton Dynamics of Donor-Orthogonal Acceptor Conjugated Polymers: Reducing the Singlet-Triplet Energy Gap

Accepted version
Peer-reviewed

Type

Article

Change log

Authors

Freeman, DME 
Musser, AJ 
Frost, JM 
Stern, HL 
Forster, AK 

Abstract

The presence of energetically low-lying triplet states is a hallmark of organic semiconductors. Even though they present a wealth of interesting photophysical properties, these optically dark states significantly limit optoelectronic device performance. Recent advances in emissive charge-transfer molecules have pioneered routes to reduce the energy gap between triplets and "bright" singlets, allowing thermal population exchange between them and eliminating a significant loss channel in devices. In conjugated polymers, this gap has proved resistant to modification. Here, we introduce a general approach to reduce the singlet-triplet energy gap in fully conjugated polymers, using a donor-orthogonal acceptor motif to spatially separate electron and hole wave functions. This new generation of conjugated polymers allows for a greatly reduced exchange energy, enhancing triplet formation and enabling thermally activated delayed fluorescence. We find that the mechanisms of both processes are driven by excited-state mixing between π-π*and charge-transfer states, affording new insight into reverse intersystem crossing.

Description

Keywords

0303 Macromolecular and Materials Chemistry

Journal Title

Journal of the American Chemical Society

Conference Name

Journal ISSN

0002-7863
1520-5126

Volume Title

Publisher

American Chemical Society
Sponsorship
Engineering and Physical Sciences Research Council (EP/M005143/1)
Engineering and Physical Sciences Research Council (EP/M01083X/1)
Engineering and Physical Sciences Research Council (EP/P007767/1)
European Research Council (679789)
Part of this work was funded by EU project 679789 – 455 CONTREX, EC H2020 SYNCHRONICS (643238), EC H2020 SOLEDLIGHT (643791) and EPSRC (EP/M005143/1) A.J.M. was supported by the EPSRC (EP/456M01083X). J.M.F. was supported by EPSRC (EP/K016288/1). F.C. is a Royal Society Wolfson Research Merit Award holder. H.L.S. was supported by the Winton Programme 457 for the Physics of Sustainability. We are grateful to the Imperial College High Performance Computing Service (doi: 10.14469/hpc/2232).