A general purpose reporter for cations: absorption, fluorescence and electrochemical sensing of zinc(ii)

Abstract

A fluorescent sensor has been synthesized that comprises a pyrene moiety tethered to a [2,2′:6′,2″]-terpyridyl ligand via a diethynylated thiophene linker. This multicomponent supermolecule is highly emissive in solution but addition of Zn²⁺ cations results in a drastic decrease in the fluorescence yield. Complexation between Zn²⁺ cations and the vacant terpyridyl ligand has been confirmed by NMR spectroscopy and by electrospray mass spectrometry. The ES-MS results provide strong support for the formation of both 1 ∶ 1 and 1 ∶ 2 (metal ∶ ligand) complexes in solution. Complexation is further evidenced by a pronounced shift in the absorption spectrum, by the appearance of a long-wavelength band in the fluorescence spectrum and by cyclic voltammetry. On the basis of UV-visible spectrophotometric titrations, overall binding constants of logβ₁ ≈ 5.1 and logβ₂ ≈ 9.9 were derived for the 1 ∶ 1 and 1 ∶ 2 complexes, respectively, in acetonitrile solution. The possible application of this system as a generic chemical sensor for cationic species is mentioned.