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    Lower rim isoxazole-calix[4]arene derivatives as fluorescence sensors for copper(II) ions


    Maher, Niall and Diao, Haowen and O'Sullivan, Justine and Fadda, Elisa and Heaney, Frances and McGinley, John (2015) Lower rim isoxazole-calix[4]arene derivatives as fluorescence sensors for copper(II) ions. Tetrahedron, 71 (49). pp. 9223-9233. ISSN 0040-4020

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    Abstract

    Chemosensors designed around a calix[4]arene scaffold, possessing distal isoxazole nuclei as potential recognition sites in conjugation with fluorogenic reporting moieties, have been synthesised and their molecular structures determined by single crystal X-ray analysis. PIC (pyrene-isoxazole-calix[4]arene) and AIC (anthracene-isoxazole-calix[4]arene) are found to be selective and sensitive for the recognition of copper(II) ions over a range of divalent metal ions in a spectrofluorometric study in acetonitrile. Following exposure to copper(II) ions the fluorescence emission intensity of the host was dramatically quenched, in contrast there were no significant shifts to the UV–vis spectra. 1H NMR spectroscopic studies could not provide unambiguous evidence for the mode of ion recognition. Hybrid Density Functional Theory (DFT) calculations for the PIC-copper(II) complex suggests that the metal ion adopts tetrahedral geometry in an acetonitrile solution, while a distorted square pyramidal coordination is also possible in the absence of solvent molecules. Both of these binding conformations cause the disruption of the pyrene–pyrene stacking, consistent with the observed fluorescence quenching.

    Item Type: Article
    Keywords: Calix[4]arene; Isoxazole; NOAC chemistry; Fluorescence; X-ray structure; DFT;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Item ID: 10767
    Identification Number: https://doi.org/10.1016/j.tet.2015.10.045
    Depositing User: Dr. Frances Heaney
    Date Deposited: 02 May 2019 14:43
    Journal or Publication Title: Tetrahedron
    Publisher: Elsevier
    Refereed: Yes
    URI:

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