Synthesis and photophysical and cation-binding properties of mono- and tetranaphthylcalix[4]arenes as highly sensitive and selective fluorescent sensors for sodium.

Abstract

The syntheses and properties of two calixarene-based fluorescent molecular sensors are reported. These comprise tert-butylcalix[4]arene either with one appended fluorophore and three ester groups (Calix-AMN1). or with four appended fluorophores (Calix-AMN4). The fluorophore is 6-acyl-2-methoxynaphthalene (AMN), which contains an electron-donating substituent (methoxy group) conjugated to an electron-withdrawing substituent (carbonyl group); this allows photoinduced charge transfer (PCT) to occur upon excitation. The investigated fluoroionophores thus belong to the family of PCT fluorescent molecular sensors. In addition to the expected red shifts of the absorption and emission spectra upon cation binding, a drastic enhancement of the fluorescence quantum yield-in an "off- on" fashion comparable to that seen in photoinduced electron transfer (PET) molecular sensors-was observed. For Calix-AMN1. it increases from 10(-3) for the free ligand to 0.68 for the complex with Ca2+. This exceptional behaviour can be interpreted in terms of the relative locations of the npi* and pipi* levels, which depend on the charge density of the bound cation. For Calix-AMN4. in addition to the photophysical effects observed for Calix-AMN1, interactions between the chromophores by complexation with some cations have been found in the ground state (hypochromic effect) and in the excited state (excimer formation). Steady-state fluorescence anisotropy measurements for the system Na+ is included in Calix-AMN4, show a depolarization effect due to energy transfer (homotransfer) between the fluorophores. Regarding the complexing properties, a high selectivity for Na+ over K+, Li+, Ca2+ and Mg2+ was observed in ethanol and ethanol-water mixtures. The selectivity (Na+/other cations) expressed as the ratio of the stability constants was found to be more than 400.