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The excited-state dynamics of the radical anions of cyanoanthracenes

Published in Physical Chemistry Chemical Physics. 2022, vol. 24, no. 1, p. 568-577
Abstract The radical anion of 9,10-dicyanoanthracene (DCA) has been suggested to be a promising chromophore for photoredox chemistry, due to its nanosecond excited-state lifetime determined from indirect measurements. Here, we investigate the excited-state dynamics of the radical anion of three cyanoanthracenes, including DCA˙−, produced by photoinduced electron transfer in liquid using both pump–probe and pump–pump probe transient electronic absorption spectroscopy. All three excited radical ions are characterised by a 3–5 ps lifetime, due to efficient non-radiative deactivation to the ground state. The decay pathway most probably involves D1/D0 conical intersection(s), whose presence is favoured by the enhanced flexibility of the radical anions relative to their neutral counterparts. The origin of the discrepancy with the nanosecond lifetime of DCA˙−* reported previously is discussed. These very short lifetimes limit, but do not preclude, photochemical applications of the cyanoanthracene anions.
PMID: 34904984
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Research group Groupe Vauthey
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BECKWITH, Joseph, ASTER, Alexander, VAUTHEY, Eric. The excited-state dynamics of the radical anions of cyanoanthracenes. In: Physical chemistry chemical physics, 2022, vol. 24, n° 1, p. 568-577. doi: 10.1039/D1CP04014F https://archive-ouverte.unige.ch/unige:157670

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Deposited on : 2022-01-03

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