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    We synthesised thionium-ion embedded aromatic porphyrinoids: a free-base 5-thiaporphyrinium cation and its zinc complex. The sulphur atom effectively participates in the macrocyclic π-conjugation. Fluorescence quantum yields of thiaporphyrinium cations were lower than 1% unlike oxaporphyrinium cations. Detailed photophysical analysis and DFT calculations clarified the vibrational mode regarding the out-of-plane motion of the sulphur atom induced ultrafast quenching of the excited state in comparison to the corresponding oxaporphyrinium cations.


    Asahi Takiguchi, Naoto Inai, Seongsoo Kang, Masaya Hagai, Seokwon Lee, Takeshi Yanai, Dongho Kim, Hiroshi Shinokubo. 5-Thiaporphyrinium cation: effect of sulphur incorporation on excited state dynamics. Chemical communications (Cambridge, England). 2022 May 17;58(40):5956-5959

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    PMID: 35438694

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