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Ion sensing with a calix[4]arene bifunctional receptor with thiosemicarbazone moieties and naphthalene chromophore

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Abstract

We have developed a chemosensor using calix[4]arene, which features a thiosemicarbazone binding/sensing unit and a naphthalene chromogenic group. Our objective was to understand the intricate binding affinity of these chemosensors towards a diverse range of anions and cations using UV–Visible, HNMR and IR spectroscopic techniques. We showed that this chemosensor can form complexes with Ag(I) or Cu (II) and to detect CN− or F− ions by deprotonation of thiosemicarbazone. To understand the behavior of these interactions, our analysis provides information on the interaction patterns between the receptors and the ions. The sulfur and imine nitrogen on the thiosemicarbazone substituent are vital sites of engagement for cation ions, as evidenced by the observed changes in IR. HNMR studies for interaction with anions indicate the involvement of the thiosemicarbazone hydrogens. Interactions taking place during complex formation with cations lead to changes in the color of the solution or solid complex, easy to follow by UV–Vis spectrocopy. Our study improves the understanding of molecular recognition of this chemosensor, highlighting its potential for ion- selective detection.

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Acknowledgements

Our thanks are to FONDECYT Grants: 1151310 and to CONICYT (Beca Doctorado Nacional 21130501 and 21130502) for support. Dr. Horacio Gomez-Machuca thanks are to ANID for postdoctoral project FONDECYT grants: 3210140. We would like to dedicate this work to the memory of Dr. Carolina Jullian Matthaei.

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  1. Departamento de Química Orgánica y Fisicoquímica, Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Olivos 1007, Independencia, Santiago, Chile

    Horacio Gómez-Machuca, Cinthia Quiroga-Campano, Hernán Pessoa-Mahana & Claudio Saitz

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  1. Horacio Gómez-Machuca
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  2. Cinthia Quiroga-Campano
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  3. Hernán Pessoa-Mahana
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H. G.-M. wrote the main manuscript text and carried out the methodology and investigation. H. G.-M prepared figures, tables and suplementary information. C. S. and H. G.-M. were involved in conceptualization, C. Q.-C. supervised the experiments in spectroscopic techniques, especially NMR. H. P.-M., C. S., and C. Q.-C. reviewed, edited, and supervised the manuscript. C. S. was in charge of project management and was the main source of fund acquisition.

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Correspondence to Horacio Gómez-Machuca or Claudio Saitz.

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Gómez-Machuca, H., Quiroga-Campano, C., Pessoa-Mahana, H. et al. Ion sensing with a calix[4]arene bifunctional receptor with thiosemicarbazone moieties and naphthalene chromophore. J Incl Phenom Macrocycl Chem 104, 161–170 (2024). https://doi.org/10.1007/s10847-024-01239-z

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