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Thermodynamic equilibrium between locally excited and charge-transfer states through thermally activated charge transfer in 1-(pyren-2′-yl)-o-carborane

Ji, Lei; Riese, Stefan; Schmiedel, Alexander; Holzapfel, Marco; Fest, Maximillian; Nitsch, Jörn; Curchod, Basile F.E.; Friedrich, Alexandra; Wu, Lin; Al Mamari, Hamad H.; Hammer, Sebastian; Pflaum, Jens; Fox, Mark A.; Tozer, David J.; Finze, Maik; Lambert, Christoph; Marder, Todd B.

Thermodynamic equilibrium between locally excited and charge-transfer states through thermally activated charge transfer in 1-(pyren-2′-yl)-o-carborane Thumbnail


Authors

Lei Ji

Stefan Riese

Alexander Schmiedel

Marco Holzapfel

Maximillian Fest

Jörn Nitsch

Alexandra Friedrich

Lin Wu

Hamad H. Al Mamari

Sebastian Hammer

Jens Pflaum

Maik Finze

Christoph Lambert

Todd B. Marder



Abstract

Reversible conversion between excited-states plays an important role in many photophysical phenomena. Using 1-(pyren-2′-yl)-o-carborane as a model, we studied the photoinduced reversible charge-transfer (CT) process and the thermodynamic equilibrium between the locally-excited (LE) state and CT state, by combining steady state, time-resolved, and temperature-dependent fluorescence spectroscopy, fs- and ns-transient absorption, and DFT and LR-TDDFT calculations. Our results show that the energy gaps and energy barriers between the LE, CT, and a non-emissive ‘mixed’ state of 1-(pyren-2′-yl)-o-carborane are very small, and all three excited states are accessible at room temperature. The internal-conversion and reverse internal-conversion between LE and CT states are significantly faster than the radiative decay, and the two states have the same lifetimes and are in thermodynamic equilibrium.

Journal Article Type Article
Acceptance Date Mar 24, 2022
Online Publication Date Apr 19, 2022
Publication Date 2022
Deposit Date May 4, 2022
Publicly Available Date May 4, 2022
Journal Chemical Science
Print ISSN 2041-6520
Electronic ISSN 2041-6539
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 13
Pages 5205-5219
DOI https://doi.org/10.1039/d1sc06867a
Public URL https://durham-repository.worktribe.com/output/1208889

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