Synthesis and specific fluoride binding properties of expanded dithiacalixphyrins

Abstract

Expanded dithiacalixphyrins with the N₂S₂ core containing two sp³ and three sp²meso-carbons have been prepared by condensation of one equivalent of butene-2,3-diyl-bisthiophene-2,5-diyl-bis(p-methoxyphenylmethanol) with one equivalent of 5,5′-dialkyldipyrromethane under mild acid catalyzed conditions in decent yields. The expanded dithiacalixphyrins were characterized by HR-MS, 1D and 2D NMR techniques and the structure of one of the expanded dithiacalixphyrin macrocycles was solved by X-ray crystallography. The crystal structure analysis indicated that the macrocycle is highly distorted and attains a boat shaped structure. The expanded thiacalixphyrins showed a specific sensing ability for F⁻ ions over other anions as judged from absorption, NMR and mass spectral studies.