Peripherally hexachlorinated meso-triphenyl subporphyrin 4 was prepared by chlorination of meso-triphenyl subporphyrin 1 with N-chlorosuccinimide and was effectively transformed to hexasulfanylated subporphyrins 5-8 via nucleophilic aromatic substitution (S(N)Ar) reactions with the corresponding thiols under basic conditions. The structures of 5-8 have been all well characterized by single-crystal X-ray analysis. (1)H NMR studies indicated that the meso-phenyl substituents undergo restricted rotation for 5-8, while the β-sulfanyl substituents are conformationally flexible in 5, 6, and 8, and are strictly regulated to an anti-conformation in 7. Judging from the absorption spectra, the oxidation and reduction potentials, and the DFT calculations, the substituent effects decrease in the order of 5>6>7>8. Subporphyrin 8 effectively captures C60 in a 1:1 manner in [D8 ]toluene solution.
Keywords: SNAr reaction; fullerenes; porphyrinoids; subporphyrins; sulfanylation.
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