New oxacalix[4]arene carboxylate detects viologen in protic media

We demonstrate that Ullman fragment-coupling can be used to synthesise an oxacalix[4]arene monocarboxylic acid, which provides easy access to its water-soluble carboxylato derivatives. Crystallographic and computational data suggest that the new carboxyl-substituted oxacalix[4]arene adopts a 1,3-alternate conformation both in the solid-state and in methanol solution. Its water-soluble tetrabutylammonium derivate can detect the herbicide paraquat at neutral pH in aqueous media (K-a = 111 +/- 3 M-1) and in methanol (K-a = 2020 +/- 70 M-1).