Aza- and Mixed Thia/Aza-Macrocyclic Receptors with Quinoline-Bearing Pendant Arms for Optical Discrimination of Zinc(II) or Cadmium(II) Ions

Abstract

The synthesis and coordination properties of two fluorescent chemosensors, featuring [9]aneN₃ (1,4,7-triazacyclononane; L1) and [12]aneNS₃ (1-aza-4,7,10-trithiacyclododecane; L2) as receptor units, and a quinoline pendant arm with an amide group as a functional group spacer are described. The optical responses of L1 and L2 in the presence of several metal ions were analysed in MeCN/H₂ O (1 : 4 v/v) solutions. A selective chelation enhancement of fluorescence (CHEF) effect was observed in the presence of Zn²⁺ in the case of L1, and in the presence of Cd²⁺ in the case of L2, following the formation of a 1 : 1 and a 1 : 2 metal/ligand complex, respectively, which was also confirmed by potentiometric measurements. ¹ H and ¹³ C NMR measurements in CD₃ CN/CDCl₃ in combination with molecular mechanics calculations show that for both complexes of L1 and L2 with Zn²⁺ and Cd²⁺ , respectively, the coordination of the carbonyl group from the pendant arm could be the origin of the observed optical selectivity.

Keywords: cadmium; fluorescent sensors; macrocycles; quinolines; zinc.