Recognition of silver cations by multifarene[2,2] chemosensors with unexpected fluorescence response

Abstract

Fluorescent chemosensors based on a new macrocyclic compound, multifarene[2,2], with modification by triazole-linked pyrene or anthracene were synthesized. These macrocyclic sensors exhibited high affinity and selectivity toward Ag⁺ over other metal ions, with ratiometric or enhanced response of their fluorescence emissions depending upon the substituent species for coordination to Ag⁺, and an unexpected response to a concentration threshold of the metal cations was discovered. The experimental evidences of fluorescence spectra, ¹H NMR titration, IR spectra, and high-resolution mass spectra suggested the coordination behaviors of the sensors with Ag⁺, that is, the 1:1 complexes were formed with moderate association constants of about 10⁵ L·mol^-1, and the sulfur atoms on macrocyclic ligand should affinite to the metal cations. Energy-minimized structures and frontier orbitals were estimated by quantum chemical calculations with a view to rationalizing the fluorescence response of the multifarene[2,2] sensors upon binding to Ag⁺.

Keywords: Fluorescent chemosensor; Molecular recognition; Multifarene[2,2]; Silver cations; Supramolecular chemistry.