A multi-responsive crown ether-based colorimetric/fluorescent chemosensor for highly selective detection of Al³⁺,...

A novel multi-response chemosensor L based on coumarin-chalcone-crown ether was designed and synthesized, which exhibited a high selectivity for the colorimetric detecting Al³⁺ and Cu²⁺ and fluorescent recognizing Al³⁺ and Mg²⁺ in ethanol. L can monitor Al³⁺ and Cu²⁺ via distinct color changes from a slight yellow to pink and to orange, respectively. The sensor L can also monitor Al³⁺ and Mg²⁺ by fluorescence emission responses at 592 nm and 547 nm with low detection limits of 0.31 μM and 0.23 μM, respectively. The selectivity of L toward Al³⁺, Cu²⁺ and Mg²⁺ was not interfered by a large number of coexisting ions and was found to be reversible. By means of spectrometric titration, Job's plot, mass spectrometry, ¹H NMR titration and IR spectroscopy analysis, it was unanimously confirmed that the sensor L had a stoichiometric ratio of 1:1 with Cu²⁺ and Mg²⁺, and 1:2 with Al³⁺. The order of the stability of the complexes formed by L and Al³⁺, Cu²⁺, Mg²⁺ was as follows: L-Al³⁺ > L-Cu²⁺ > L-Mg²⁺. At the same time, some possible bonding modes and sensing mechanisms were further proposed, and the optimized structure of the sensor L and its sensing mechanism for Al³⁺, Cu²⁺ and Mg²⁺ were confirmed by the calculations of DFT/B3LYP and TD-DFT methods in a suite of Gaussian 09 programs.