Dimers CEJ 2021 Accepted Manuscript.pdf (1.37 MB)

Conformational dependence of triplet energies in rotationally‐hindered N‐ and S‐heterocyclic dimers: new design and measurement rules for high triplet energy OLED host materials

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journal contribution
posted on 16.02.2021, 09:08 by Iain Wright, Andrew Danos, Stephanie Montanaro, Andrei S Batsanov, Andrew P Monkman, Martin R Bryce
A series of four heterocyclic dimers has been synthesized, with twisted geometries imposed across the central linking bond by ortho‐alkoxy chains. These include two isomeric bicarbazoles, a bis(dibenzothiophene‐S,S‐dioxide) and a bis(thioxanthene‐S,S‐dioxide). Spectroscopic and electrochemical methods, supported by density functional theory, have given detailed insights into how para‐ vs. meta‐ vs. broken conjugation, and electron‐rich vs. electron‐poor heterocycles impact the HOMO‐LUMO gap and singlet and triplet energies. Crucially for applications as OLED hosts, the triplet energy (ET) of these molecules was found to vary significantly between dilute polymer films and neat films, related to conformational demands of the molecules in the solid state. One of the bicarbazole species shows a variation in ET of 0.24 eV in the different media – sufficiently large to “make‐or‐break” an OLED device – with similar discrepancies found between neat films and frozen solution measurements of other previously reported OLED hosts. From consolidated optical and optoelectronic investigations of different host/dopant combinations, we identify that only the lower ET values measured in neat films give a reliable indicator of host/guest compatibility. This work also provides new molecular design rules for obtaining very high ET materials and controlling their HOMO and LUMO energies.


The Energy Agenda: Exciplex blend small-molecule OLEDs; high performance fluorescent devices from E-type triplet harvesting

Engineering and Physical Sciences Research Council

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RSC Research Fund grant numbers RF18-5353 and RF19-2751

HyperOLED project from the European Union’s Horizon 2020 research and innovation program under grant agreement number 732013



  • Science


  • Chemistry

Published in

Chemistry – A European Journal




AM (Accepted Manuscript)

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© Wiley

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This is an Open Access Article. It is published by Wiley under the Creative Commons Attribution 4.0 International Licence (CC BY 4.0). Full details of this licence are available at: https://creativecommons.org/licenses/by/4.0/

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Dr Iain Wright. Deposit date: 15 February 2021