This paper presents a novel series of chemically stable and redox-switchable 20π, 19π, and 18π5,10,15,20-tetraaryl-5,15-diazaporphyrinoids (TADAPs) that have two alkyl-chain straps above and below the diazaporphyrin ring. Three types of doubly strapped TADAPs were prepared as nickel(II) complexes using meso-N-(2,6-dihydroxyphenyl)-substituted TADAP and the corresponding aliphatic diacids as precursors. Theoretical calculations revealed that regardless of their oxidation states, all strapped TADAPs had essentially flat π-planes. It was found that the alkyl-chain straps slightly affected the optical and electrochemical properties of the DAP rings, particularly in the oxidized forms. 1H NMR spectroscopy was used to evaluate the antiaromatic character of the 20πTADAPs and the aromatic character of the 18πTADAP dications, and it was observed that they displayed paratropic and diatropic ring-current effects, respectively, on the chemical shifts of methylene protons in the spatially separated alkyl chains. The degree of shielding and deshielding depended on the position of the methylene units; it decreased with increase in separation from the π-plane and central axis of the porphyrin ring. The NMR experiments also revealed that the degree of the diatropic ring currents was clearly related to the π-electron density of the porphyrin ring; the ring-current effects decreased as the charge increased from 0 to +2. These findings are also qualitatively supported by the nucleus-independent chemical shifts.
All Science Journal Classification (ASJC) codes
- Organic Chemistry