Affiliation:
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.
Funder
Henan University
National Natural Science Foundation of China
China Postdoctoral Science Foundation
Henan Province Postdoctoral Science Foundation
Henan Province Scientific Research Foundation of Higher Education
State Key Laboratory of Catalysis in DICP
Reference42 articles.
1. Synthesis and functionalization of porphyrins through organometallic methodologies;Hiroto;Chem. Rev.,2017
2. Nonplanar porphyrins: Synthesis, properties, and unique functionalities;Ishizuka;Chem. Soc. Rev.,2022
3. Porphyrin-based supramolecular polymers;Lee;Chem. Soc. Rev.,2023
4. Studies of the reduction of the nickel(II) complex of 5,10,15,20-tetraphenyl-21-thiaporphyrin to form corresponding nickel(I) complexes;Chmielewski;Inorg. Chem.,1989
5. Palladium complexes of 21-thiaporphyrin: Syntheses and characterization;Lisowski;Inorg. Chem.,1994