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Updated: Jun 18, 2025

Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method
Published on: July 19, 2019
Hydrogen Atom Abstraction and Reduction Study of 21-Thiaporphyrin and 21,23-Dithiaporphyrin
Xiao-Rui Ren1, Kang Xing1, Teng Liu1
1Key Laboratory for Special Functional Materials of Ministry of Education, National and Local Joint Engineering Research Center for High-Efficiency Display and Lighting Technology, School of Nanoscience and Materials Engineering, Henan University, Kaifeng 475004, China.
Abstract:
The metal-free porphyrins protonation has gained interest over five decades because its structure modification and hardly monoacid intermediate isolation. Here, upon the hydrogen atom abstraction processes, one step diproptonated H3STTP(BF4)2 (STTP = 5,10,15,20-tetraphenyl-21-thiaporphyrin) (3) and stepwise protonated HS2TTPSbCl6 (5) and diprotonated H2S2TTP(BF4)2 (6) (S2TTP = 5,10,15,20-tetraphenyl-21,23-thiaporphyrin) compounds were obtained using HSTTP and S2TTP with oxidants. The closed-shell protonated compounds were fully characterized using XRD, UV-vis, IR and NMR spectra. In addition, the reduced 19π compounds [K(2,2,2)]HSTTP (2) and [K(2,2,2)]S2TTP (7) were synthesized by the ligands with reductant KC8 in THF solution. These two open-shell compounds were characterized with UV-vis, IR and EPR spectroscopies. The semiempirical ZINDO/S method was employed to analyze the HOMO/LUMO gap lever and identify the electronic transitions of the UV-vis spectra of the closed- and open-shell porphyrin compounds.
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