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
Affiliations
Xiao-Rui Ren
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
Kang Xing
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
Teng Liu
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
Ronghui Cao
College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471934, China
Li-Long Dang
College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471934, China
Feng Bai
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
Peng-Cheng Duan
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
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.
