A computational study of I-BODIPY (2-ethyl-4,4-difluoro-6,7-diiodo-1,3-dimethyl-4-bora-3a,4a-diaza-s-indacene) has been carried out to investigate its key photophysical properties as a potential triplet photosensitizer capable of generating singlet oxygen. Multireference CASPT2 and CASSCF methods have been used to calculate vertical excitation energies and spin-orbit couplings (SOCs), respectively, in a model (mono-iodinated BODIPY) molecule to assess the applicability of the single-reference second-order algebraic diagrammatic construction, ADC(2), method to this and similar molecules. Subsequently, time-dependent density functional theory (TD-DFT), possibly within the Tamm-Dancoff approximation (TDA), using several exchange-correlation functionals has been tested on I-BODIPY against ADC(2), both employing a basis set with a two-component pseudopotential on the iodine atoms. Finally, the magnitudes of SOC between excited electronic states of all types found have thoroughly been discussed using the Slater-Condon rules applied to an arbitrary one-electron one-center effective spin-orbit Hamiltonian. The geometry dependence of SOCs between the lowest-lying states has also been addressed. Based on these investigations, the TD-DFT/B3LYP and TD-DFT(TDA)/BHLYP approaches have been selected as the methods of choice for the subsequent nuclear ensemble approach absorption spectra simulations and mixed quantum-classical trajectory surface hopping (TSH) molecular dynamics (MD) simulations, respectively. Two bright states in the visible spectrum of I-BODIPY have been found, exhibiting a redshift of the main peak with respect to unsubstituted BODIPY caused by the iodine substituents. Excited-state MD simulations including both non-adiabatic effects and SOCs have been performed to investigate the relaxation processes in I-BODIPY after its photoexcitation to the S 1 $$ {\mathrm{S}}_1 $$ state. The TSH MD simulations revealed that intersystem crossings occur on a time scale comparable to internal conversions and that after an initial phase of triplet population growth a "saturation" is reached where the ratio of the net triplet to singlet populations is about 4:1. The calculated triplet quantum yield of 0.85 is in qualitative agreement with the previously reported experimental singlet oxygen generation yield of 0.99 ± $$ \pm $$ 0.06.

Faculty of Science Department of Physical and Macromolecular Chemistry Charles University Prague 2 Czech Republic

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Prague 6 Czech Republic

J Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences Prague 8 Czech Republic

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