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

The result's identifiers

  • Result code in IS VaVaI

    <a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F18%3A00494128" target="_blank" >RIV/61388955:_____/18:00494128 - isvavai.cz</a>

  • Result on the web

    <a href="http://dx.doi.org/10.1021/acs.jpca.8b05311" target="_blank" >http://dx.doi.org/10.1021/acs.jpca.8b05311</a>

  • DOI - Digital Object Identifier

    <a href="http://dx.doi.org/10.1021/acs.jpca.8b05311" target="_blank" >10.1021/acs.jpca.8b05311</a>

Alternative languages

  • Result language

    angličtina

  • Original language name

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

  • Original language description

    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(Ï€) participation in the corrole Ï€-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 (ii) opening new SOC pathways whereby CT triplet character is admixed into both Q singlet excited states. In addition, SOC between the higher Q singlet and the Soret triplet is enhanced as the iodine participation in frontier corrole Ï€-orbitals increases. Our observations that iodination of the chromophore periphery affects the whole photocycle by changing the electronic structure, spin-orbit coupling, and the density of states rationalize the ´´heavy-atom effect´´ and have implications for controlling excited-state dynamics in a range of triplet photosensitizers.

  • Czech name

  • Czech description

Classification

  • Type

    J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database

  • CEP classification

  • OECD FORD branch

    10403 - Physical chemistry

Result continuities

  • Project

    <a href="/en/project/GA17-01137S" target="_blank" >GA17-01137S: Electron Transfer in (Bio)Molecular Systems: Time-Resolved Vibrational Spectroscopy and Theory</a><br>

  • Continuities

    P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Others

  • Publication year

    2018

  • Confidentiality

    S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Data specific for result type

  • Name of the periodical

    Journal of Physical Chemistry A

  • ISSN

    1089-5639

  • e-ISSN

  • Volume of the periodical

    122

  • Issue of the periodical within the volume

    37

  • Country of publishing house

    US - UNITED STATES

  • Number of pages

    11

  • Pages from-to

    7256-7266

  • UT code for WoS article

    000445711900002

  • EID of the result in the Scopus database

    2-s2.0-85053197585