Hydrogen Atom Abstraction and Reduction Study of 21-Thiaporphyrin and 21,23-Dithiaporphyrin

Xiao-Rui Ren; Kang Xing; Teng Liu; Ronghui Cao; Li-Long Dang; Feng Bai; Peng-Cheng Duan

doi:10.3390/molecules29143424

Hydrogen Atom Abstraction and Reduction Study of 21-Thiaporphyrin and 21,23-Dithiaporphyrin

Molecules. 2024 Jul 22;29(14):3424. doi: 10.3390/molecules29143424.

Authors

Xiao-Rui Ren¹, Kang Xing¹, Teng Liu¹, Ronghui Cao², Li-Long Dang², Feng Bai¹, Peng-Cheng Duan¹

Affiliations

¹ Key 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.
² College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471934, 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.

Keywords: X-ray diffraction; ZINDO/S calculation; hydrogen atom abstraction; reduction; thiaporphyrins.

Grants and funding

This research was funded by the Henan University, the National Natural Science Foundation of China (22201060, 21771055, and U21A2085), the China Postdoctoral Science Foundation (2022M711032), the Henan Province Postdoctoral Science Foundation (202101024), the Henan Province Scientific Research Foundation of Higher Education (22A150034) and the State Key Laboratory of Catalysis in DICP (N-23-13).