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Isoxazolo‐pyrene tethered calixarenes selectively detect copper(II) ions without interference from related perchlorate ions. The fluorescence emission of the probes, synthesised by nitrile oxide alkyne cycloaddition, and characterised by spectroscopic and crystallographic data, is rapidly reduced by Cu(II) ions. Detection limits are in the micromolar or sub‐micromolar range (0.3–3.6 μM) based on a 1 : 1 sensor:analyte interaction. Voltammetric behaviour and 1H NMR data provide new insights into the sensing mechanism which is dependent on the calixarene substitution pattern. When the calixarene lower rim is fully substituted, Cu(II) detection occurs through a traditional chelation mechanism. In contrast, for calixarenes 1,3‐disubstituted on the lower rim, detection takes place through a chemodosimetric redox reaction. The isolation of a calixdiquinone from the reaction with excess Cu(ClO4)2 provides confirmation that the sensor–analyte interaction culminates in irreversible sensor oxidation.
O'Sullivan, J., Colleran, J., Twamley, B. & Heaney, F. (2019). Highly Selective Fluorimetric Turn‐Off Detection of Copper(II) by Two Different Mechanisms in Calixarene‐Based Chemosensors and Chemodosimeters. CHEMPLUSCHEM, 84(10).p. 1610-1622. doi:0.1002/cplu.201900448
Irish Research Council