Tricyclic octaurea “Temples” for the recognition of polar molecules in water

Abstract

Two water-soluble tricyclic “Temple” macrocycles featuring pyrene roof/floor units and bis-urea spacers have been synthesised and studied as receptors for aromatic compounds in aqueous media. The tricycles show good selectivity for methylated purine alkaloids such as caffeine versus unsubstituted heterocycles such as adenine and indole. Binding is signalled by major changes in fluorescence, apparently due to the break-up of intramolecular excimers. The formation of excimers implies cavity collapse in the absence of guests explaining why, unlike an earlier relative, these receptors do not bind carbohydrates. Naphthalenediimides (NDIs) have also been studied as geometrically complementary guests, and indeed bind especially strongly (K_a > 10⁷ M⁻¹); this powerful and selective association suggests potential applications in supramolecular self-assembly.