5,5,15,15-Tetraoxo-5,15-Dithiaporphyrin as a Highly Electron-Deficient Porphyrinic Ligand.
Atsumi YagiTakeshi KondoDaisuke YamashitaNaruhiko WachiHiroto OmoriNorihito FukuiTakahisa IkeueHiroshi ShinokuboPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2019)
Oxidation of 5,15-dithiaporphyrin with meta-chloroperbenzoic acid afforded the corresponding S,S-tetraoxide in good yield. The resultant 5,5,15,15-tetraoxo-5,15-dithiaporphyrin exhibited the highly electron-deficient nature as elucidated by the electrochemical analysis and theoretical calculations. Treatment of tetraoxodithiaporphyrin with zinc(II) acetate and nickel(II) acetate provided the corresponding metal complexes efficiently. Owing to its enhanced Lewis acidity of the metal center by the electron-deficient ligand, the nickel complex underwent facile axial ligation to form pentacoordinate and hexacoordinate high-spin (S=1) complexes in solution and solid, respectively. The binding constant of pyridine to the NiII center was significantly higher than those of conventional porphyrin NiII complexes. Temperature-dependent magnetic susceptibility measurements of the high-spin NiII complex revealed the presence of weak ferromagnetic interactions.
Keyphrases
- metal organic framework
- electron transfer
- density functional theory
- room temperature
- oxide nanoparticles
- reduced graphene oxide
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- molecular dynamics
- photodynamic therapy
- ionic liquid
- wild type
- electron microscopy
- single cell
- molecular dynamics simulations
- carbon nanotubes
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- transition metal
- high resolution