Theoretical Investigation of the Effect of Alkylation and Bromination on Intersystem Crossing in BODIPY-Based Photosensitizers

0548402 - ÚOCHB 2022 RIV US eng J - Článek v odborném periodiku
Baig, M. W. - Pederzoli, M. - Kývala, Mojmír - Cwiklik, Lukasz - Pittner, J.
Theoretical Investigation of the Effect of Alkylation and Bromination on Intersystem Crossing in BODIPY-Based Photosensitizers.
Journal of Physical Chemistry B. Roč. 125, č. 42 (2021), s. 11617-11627. ISSN 1520-6106. E-ISSN 1520-5207
Institucionální podpora: RVO:61388963
Klíčová slova: bromine * atoms * density functional theory
Obor OECD: Physical chemistry
Impakt faktor: 3.466, rok: 2021
Způsob publikování: Omezený přístup
https://doi.org/10.1021/acs.jpcb.1c05236

Halogenated and alkylated BODIPY derivatives are reported as suitable candidates for their use as photosensitizers in photodynamic therapy due to their efficient intersystem crossing (ISC) between states of different spin multiplicities. Spin–orbit couplings (SOCs) are evaluated using an effective one-electron spin–orbit Hamiltonian for brominated and alkylated BODIPY derivatives to investigate the quantitative effect of alkyl and bromine substituents on ISC. BODIPY derivatives containing bromine atoms have been found to have significantly stronger SOCs than alkylated BODIPY derivatives outside the Frank–Condon region while they are nearly the same at local minima. Based on calculated time-dependent density functional theory (TD-DFT) vertical excitation energies and SOCs, excited-state dynamics of three BODIPY derivatives were further explored with TD-DFT surface hopping molecular dynamics employing a simple accelerated approach. Derivatives containing bromine atoms have been found to have very similar lifetimes, which are much shorter than those of the derivatives possessing just the alkyl moieties. However, both bromine atoms and alkyl moieties reduce the HOMO/LUMO gap, thus assisting the derivatives to behave as efficient photosensitizers.
Trvalý link: http://hdl.handle.net/11104/0324438