Cation-Selective and Anion-Controlled Fluorogenic Behaviors of a Benzothiazole-Attached Macrocycle That Correlate with Structural Coordination Modes

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• 作者：Huiyeong Ju ; Duk Jin Chang ; Seulgi Kim ; Hyunsoo Ryu ; Eunji Lee ; In-Hyeok Park ; Jong Hwa Jung ; Mari Ikeda ; Yoichi Habata ; Shim Sung Lee
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：August 1, 2016
• 年：2016
• 卷：55
• 期：15
• 页码：7448-7456
• 全文大小：580K
• 年卷期：0
• ISSN：1520-510X

文摘

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 SO₄^2–. 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–N_tert 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.