Photophysical Heavy-Atom Effect in Iodinated Metallocorroles: Spin-Orbit Coupling and Density of States

The Journal of Physical Chemistry. a
Enrico PomaricoAntonín Vlcek

Abstract

Excited-state dynamics and electronic structures of Al and Ga corrole complexes were studied as a function of the number of β-pyrrole iodine substituents. Using spectrally broad-band femtosecond-resolved fluorescence upconversion, we determined the kinetics of the Soret fluorescence decay, the concomitant rise and subsequent decay of the Q-band fluorescence, as well as of the accompanying vibrational relaxation. Iodination was found to accelerate all involved processes. The time constant of the internal conversion from the Soret to the Q states decreases from 320-540 to 70-185 fs upon iodination. Vibrational relaxation then occurs with about 15 and 0.36-1.4 ps lifetime for iodine-free and iodinated complexes, respectively. Intersystem crossing to the lowest triplet is accelerated up to 200 times from nanoseconds to 15-24 ps; its rate correlates with the iodine p(π) participation in the corrole π-system and the spin-orbit coupling (SOC) strength. TDDFT calculations with explicit SOC show that iodination introduces a manifold of low-lying singlet and triplet iodine → corrole charge-transfer (CT) states. These states affect the photophysics by (i) providing a relaxation cascade for the Soret → Q internal conversion and cooling and...Continue Reading

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Citations

Jul 16, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Ana I RodriguesPedro T Gomes
Apr 22, 2021·Chemical Communications : Chem Comm·Woohyun LeeDavid G Churchill
Mar 14, 2020·The Journal of Physical Chemistry Letters·Aron P VeenstraManfred M Kappes
Jul 18, 2020·Inorganic Chemistry·Lars MewesMajed Chergui
Jan 24, 2019·The Journal of Physical Chemistry. a·Olivier BrämMajed Chergui

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