Excited State Dynamics of Thermally Activated Delayed Fluorescence from an Excited State Intramolecular Proton Transfer System
JOURNAL OF PHYSICAL CHEMISTRY LETTERS(2020)
Abstract
We describe the photophysical processes that give rise to thermally activated delayed fluorescence in the excited state intramolecular proton transfer (ESIPT) molecule, triquinolonobenzene (TQB). Using transient absorption and time-resolved photoluminescence spectroscopy, we fully characterize prompt and delayed emission, phosphorescence, and oxygen quenching to reveal the reverse intersystem crossing mechanism (rISC). After photoexcitation and rapid ESIPT to the TQB-TB tautomer, emission from S-1 is found to compete with thermally activated ISC to an upper triplet state, T-2 , very close in energy to S-1 and limiting photoluminescence quantum yield. T-2 slowly decays to the lowest triplet state, T-1, via internal conversion. In the presence of oxygen, T-2 is quenched to the ground state of the double proton transferred TQB-TC tautomer. Our measurements demonstrate that rISC in TQB occurs from T-2 to S-1 driven by thermally activated reverse internal conversion from T-1 to T-2 and support recent calculations by Cao et al. (Cao, Y.; Eng, J.; Penfold, T. J. Excited State Intramolecular Proton Transfer Dynamics for Triplet Harvesting in Organic Molecules. J. Phys. Chem. A 2019, 123, 2640-2649).
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