Cation-Selective and Anion-Controlled Fluorogenic Behaviors of a Benzothiazole-Attached Macrocycle That Correlate with Structural Coordination Modes
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We report how the metal cation and its counteranions cooperate in the complexation-based macrocyclic chemosensor to monitor the target metal ion via the specific coordination modes. The benzothiazolyl group bearing NO2S2-macrocycle L was synthesized, and its mercury(II) selectivity (for perchlorate salt) as a dual-probe channel (UV–vis and fluorescence) chemosensor exhibiting the largest blue shift and the fluorescence turn-off was observed. In the mercury(II) sensing with different anions, except ClO4– and NO3–, no responses for mercury(II) were observed with other anions such as Cl–, Br–, I–, SCN–, OAc–, and SO42–. A crystallographic approach for the mononuclear mercury(II) perchlorate complex [Hg(L)(ClO4)2]·0.67CH2Cl2 (1) and polymeric mercury(II) iodide complex [Hg(L)I2]n (2) revealed that the observed anion-controlled mercury(II) sensing in the fluorescence mainly stems from the endo- and exocoordination modes, depending on the anion coordinating ability, which induces either the Hg–Ntert bond formation or not. The detailed complexation process with mercury(II) perchlorate associated with the cation sensing was also monitored with the titration methods by UV–vis, fluorescence spectroscopy, and cold-spray ionization mass spectrometry.
