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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

DOI: 10.1039/D1SC06867A DOI Help

Authors: Lei Ji (Northwestern Polytechnical University; Julius-Maximilians-Universität Würzburg) , Stefan Riese (Julius-Maximilians-Universität Würzburg) , Alexander Schmiedel (Julius-Maximilians-Universität Würzburg) , Marco Holzapfel (Julius-Maximilians-Universität Würzburg) , Maximillian Fest (Julius-Maximilians-Universität Würzburg) , Jörn Nitsch (Julius-Maximilians-Universität Würzburg) , Basile F. E. Curchod (University of Durham) , Alexandra Friedrich (Julius-Maximilians-Universität Würzburg) , Lin Wu (Northwestern Polytechnical University) , Hamad H. Al Mamari (Julius-Maximilians-Universität Würzburg; Sultan Qaboos University) , Sebastian Hammer (Julius-Maximilians-Universität Würzburg) , Jens Pflaum (Julius-Maximilians-Universität Würzburg) , Mark A. Fox (University of Durham) , David J. Tozer (University of Durham) , Maik Finze (Julius-Maximilians-Universität Würzburg) , Christoph Lambert (Julius-Maximilians-Universität Würzburg) , Todd B. Marder (Julius-Maximilians-Universität Würzburg)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemical Science , VOL 492

State: Published (Approved)
Published: April 2022
Diamond Proposal Number(s): 18456

Open Access Open Access

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.

Subject Areas: Chemistry

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 25/04/2022 10:41


Discipline Tags:

Physical Chemistry Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)