Calix[4]azacrown and 4-aminophthalimide-appended calix[4]azacrown: synthesis, structure, complexation and fluorescence signaling behaviour

Abstract

The synthesis and single crystal structure of 25,27-(diamidomonoazacrown-5)-calix[4]arene (L), calix[4]arene capped by a diamide bridge in the 1,3-position on the lower rim, which forms a supramolecular dimer in the solid state via intermolecular hydrogen bonding, are described. A 4-aminophthalimide (AP) fluorophore has been regioselectively linked to the secondary amino function of the azacrown unit with a dimethylene spacer to construct N-(4-aminophthalimidoethyl)calix[4]azacrown (APL), a fluorescent sensor, via a fluorophore–spacer–receptor architecture. Fluorescence quantum yield and lifetime of APL have been measured to be lower than those of the bare fluorophore (AP) due to the photoinduced intramolecular electron transfer (PIET) between the fluorophore and the receptor moieties of the molecule. In the presence of transition metal ions, fluorescence enhancement of APL is observed suggesting the binding of the metal ion to the sensor. Complexation properties of APL with transition metal ions are investigated using UV-vis spectroscopy. A 1 : 1 stoichiometry of the complex is determined from a Job plot and the corresponding association constants for the various metal ions are evaluated. Fe³⁺ and Cu²⁺ ions have the largest association constants (K = 2.3 × 10⁵ M⁻¹ and 1.6 × 10⁵ M⁻¹ respectively) compared to other metal ions indicating that they form complexes selectively with APL.