In order to study the effect of meso -iodination of free-base corroles on their photophysical character, we designed and synthesized a series of free-base corrole derivatives F10–OH (iodine-free), F10–OH–I (mono-iodo) and F10–OH–2I (di-iodo), with different substitution patterns at the meso -position as candidates for photodynamic therapy (PDT). We employed several optical spectroscopic techniques, including time-resolved spectroscopy from a femtosecond to microsecond and singlet oxygen luminescence to study the properties of excited singlet and triplet states, as well as the singlet oxygen quantum yields. The sub-picosecond internal conversion, ～1 ps intramolecular vibrational energy redistribution, tens of ps vibrational cooling, are similar across the three corroles. The addition of one (F10–OH–I) and two iodine (F10–OH–2I) atoms to the remote aryl ring of triarylcorroles induces a 4.6-fold and 6.2-fold decrease in fluorescence quantum yields Φ _(fl) and a 2.2-fold and 4.9-fold increase in the time constant of intersystem crossing k _(ISC) . In addition, a slight increase in intersystem crossing quantum yields Φ _(T) was also observed from F10–OH to F10–OH–2I. It means the intersystem crossing is improved by the iodination, from F10–OH to F10–OH–2I, because of the heavy atom effect. However, the sample F10–OH–I, instead of F10–OH–2I, shows the highest singlet oxygen quantum yield Φ _(Δ) .
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