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

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

doi:10.1039/d1sc06867a

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

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

^*Corresponding author for this work

Chemistry

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

14 Citations (Scopus)

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.

Original language	English
Pages (from-to)	5205-5219
Number of pages	15
Journal	Chemical Science
Volume	13
Issue number	18
DOIs	https://doi.org/10.1039/d1sc06867a
Publication status	Published - Jan 1 2022

ASJC Scopus subject areas

General Chemistry

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Ji, L., Riese, S., Schmiedel, A., Holzapfel, M., Fest, M., Nitsch, J., Curchod, B. F. E., Friedrich, A., Wu, L., Al Mamari, H. H., Hammer, S., Pflaum, J., Fox, M. A., Tozer, D. J., Finze, M., Lambert, C., & Marder, T. B. (2022). Thermodynamic equilibrium between locally excited and charge-transfer states through thermally activated charge transfer in 1-(pyren-2′-yl)-o-carborane. Chemical Science, 13(18), 5205-5219. https://doi.org/10.1039/d1sc06867a

Ji, L, Riese, S, Schmiedel, A, Holzapfel, M, Fest, M, Nitsch, J, Curchod, BFE, Friedrich, A, Wu, L, Al Mamari, HH, Hammer, S, Pflaum, J, Fox, MA, Tozer, DJ, Finze, M, Lambert, C & Marder, TB 2022, 'Thermodynamic equilibrium between locally excited and charge-transfer states through thermally activated charge transfer in 1-(pyren-2′-yl)-o-carborane', Chemical Science, vol. 13, no. 18, pp. 5205-5219. https://doi.org/10.1039/d1sc06867a

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

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 {\textquoteleft}mixed{\textquoteright} 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.",

author = "Lei Ji and Stefan Riese and Alexander Schmiedel and Marco Holzapfel and Maximillian Fest and J{\"o}rn Nitsch and Curchod, {Basile F.E.} and Alexandra Friedrich and Lin Wu and {Al Mamari}, {Hamad H.} and Sebastian Hammer and Jens Pflaum and Fox, {Mark A.} and Tozer, {David J.} and Maik Finze and Christoph Lambert and Marder, {Todd B.}",

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T1 - Thermodynamic equilibrium between locally excited and charge-transfer states through thermally activated charge transfer in 1-(pyren-2′-yl)-o-carborane

AU - Ji, Lei

AU - Riese, Stefan

AU - Schmiedel, Alexander

AU - Holzapfel, Marco

AU - Fest, Maximillian

AU - Nitsch, Jörn

AU - Curchod, Basile F.E.

AU - Friedrich, Alexandra

AU - Wu, Lin

AU - Al Mamari, Hamad H.

AU - Hammer, Sebastian

AU - Pflaum, Jens

AU - Fox, Mark A.

AU - Tozer, David J.

AU - Finze, Maik

AU - Lambert, Christoph

AU - Marder, Todd B.

PY - 2022/1/1

Y1 - 2022/1/1

N2 - 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.

AB - 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.

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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

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