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A highly selective anthraquinone appended oxacalixarene receptor for fluorescent ICT sensing of F− ions: an experimental and computational study

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Abstract

A new anthraquinone appended oxacalix[4]arene (DAQOC) has been synthesized and characterized by different 1H NMR, IR, ESI-MS and 13C NMR spectroscopic techniques. This compound was explored for its sensing abilities towards various anions. DAQOC showed selective anion sensing behaviour towards F− ions which was supported by absorption as well as emission studies. Among other anions, only in the presence of F− ions, a quenching in the fluorescence emission of over 79% was observed due to changes in the intermolecular charge transfer (ICT) process. DAQOC exhibited high selectivity and good sensitivity toward F− ions in the presence of competing ions and the detection limit was found to be 1.23 µM. 1H NMR titration displays that the peak corresponding to –NH protons (at 12.91 ppm) disappears upon interaction with F−, suggesting that the sensing mechanism follows the deprotonation route. The geometrical features of F− bound oxacalixarene species were modelled by the Density Functional Theory (DFT) and NCIPlot calculations. The findings suggested that the appended substituents including nitro groups and anthraquinone can make the calix[4]arene ring electron deficient and thereby more susceptible for F− ions. Moreover, this present chemosensor has been applied for recognition of F− ions from waste water samples which is of direct practical relevance.

Graphic abstract

A new anthraquinone appended oxacalix[4]arene has been explored for its sensing abilities towards F− by absorption and emission studies. An intermolecular charge transfer mechanism has been attributed due to the deprotonation of N–H groups in DAQOC. DAQOC-F− complex is modelled by the Density Functional Theory and NCIPlot calculations.

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Acknowledgement

The authors thank the financial assistance provided by DST-SERB, New Delhi through the project scheme SERB REF. No EMR/2016/001958. Manoj Vora gratefully acknowledges the financial support received from UGC in the form of Rajiv Gandhi National Fellowship, RGNF-JRF (RGNF-2017-18-SC-GUJ-47048). V. K. Jain would like to acknowledge UGC-Mid Career Award for financial assistance (19-213/2018-BSR). Anita Kongor gratefully acknowledges the financial assistance provided by the Council of Scientific & Industrial Research (CSIR), New Delhi for Research Associateship Fellowship (File No. 09/070 (0073) 2020 EMR-I). Manthan K. Panchal gratefully acknowledges Human Resource Development Group - Council of Scientific & Industrial Research (CSIR), New Delhi for Research Associateship Fellowship (File No. 09/70 (0064) 2K19 EMR-I). The authors also acknowledge the Central Salt & Marine Chemicals Research Institute (Bhavnagar), Oxygen Healthcare-Ahmedabad (O2h), Sophisticated Analytical Instrument Facility (Panjab University) and Gujarat Forensic Sciences University (Gandhinagar), for providing instrumental facilities and UGC Infonet & Information and Library Network (INFLIBNET) (Ahmedabad) for e-journals.

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Authors and Affiliations

  1. Department of Chemistry, School of Sciences, Gujarat University, Ahmedabad, Gujarat, 380 009, India

    MANOJ VORA, ANITA KONGOR, MANTHAN PANCHAL, ASHUKUMAR VERMA, FALAK PANJWANI & VINOD JAIN

  2. CCG@CUG, School of Chemical Sciences, Central University of Gujarat, Gandhinagar, Gujarat, 382 030, India

    MOHD ATHAR

  3. CCG@CUG, Centre for Applied Chemistry, Central University of Gujarat, Gandhinagar, Gujarat, 382 030, India

    P C JHA

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  1. MANOJ VORA
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VORA, M., KONGOR, A., PANCHAL, M. et al. A highly selective anthraquinone appended oxacalixarene receptor for fluorescent ICT sensing of F− ions: an experimental and computational study. J Chem Sci 132, 156 (2020). https://doi.org/10.1007/s12039-020-01862-6

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  • DOI: https://doi.org/10.1007/s12039-020-01862-6

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