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Zn2+-Schiff’s Base Complex as an “On–Off-On” Molecular Switch and a Fluorescence Probe for Cu2+ and Ag+ Ions

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Abstract

The present study presents a thorough theoretical analysis of the electronic structure and conformational preference of Schiff’s base ligand N,N-bis(2-hydroxybenzilidene)-2,4,6-trimethyl benzene-1,3-diamine (H2L) and its metal complexes with Zn2+, Cu2+ and Ag+ ions. This study aims to investigate the behavior of H2L and the binuclear Zn2+ complex (1) as fluorescent probes for the detection of metal ions (Zn2+, Cu2+ and Ag+) using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The six conformers of the H2L ligand were optimized using the B3LYP/6–311 +  + G** level of theory, while the L−2-metal complexes were optimized by applying the B3LYP functional with the LANL2DZ/6–311 +  + G** mixed basis set. The gas-phase and solvated Enol-cis isomer (E-cis) was found to be the most stable species. The absorption spectra of the E-cis isomer and its metal complexes were simulated using B3LYP, CAM-B3LYP, M06-2X and ωB97X functionals with a 6–311 +  + G** basis set for C, O, N and H atoms and a LANL2DZ basis set for the metal ions (Zn2+, Cu2+ and Ag+). The computational results of the B3LYP functional were in excellent agreement with the experimental results. Hence, it was adopted for performing the emission calculations. The results indicated that metal complex (1) can act as a fluorescent chemosensor for the detection of Ag+ and Cu2+ ions through the mechanism of intermolecular charge transfer (ICT) and as a molecular switch “On–Off-On” via the replacement of Cu2+ by Ag+ ions, as proved experimentally.

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Availability of Data and Material/ Data Availability

The datasets generated during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

The authors acknowledge the technical support and funding by the Deanship of Scientific Research (DSR), King Abdulaziz University, Jeddah, under grant no. 140-130-1440. The authors are also grateful to the HPCC (Aziz Supercomputer) for the resources.

Funding

by the Deanship of Scientific Research (DSR), King Abdulaziz University, Jeddah, under grant no. 140–130-1440.

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Authors and Affiliations

  1. Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah, 21589, Saudi Arabia

    Shaaban A. Elroby, Saadullah G. Aziz, Abdesslem Jedidi, Walid I. Hassan & Osman I. Osman

  2. Chemistry Department, Faculty of Science, Beni-Suef University, Beni-Suef, 62511, Egypt

    Shaaban A. Elroby

  3. Chemistry Department, Faculty of Science, Taif University, Turabah, 29731, Saudi Arabia

    Bashair Abdullah Banaser

  4. Chemistry Department, Faculty of Science, University of Khartoum, P.O. Box 321, Khartoum, 11111, Sudan

    Osman I. Osman

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  1. Shaaban A. Elroby
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Contributions

Shaaban Elroby, Osman I Osman and Bashair Abdullah Banaser conceived, designed, performed the calculations enriched the research point, conducted the theoretical calculations and did the writing up of the manuscript; Abdesslem Jedidi and Walid I Hassan surveyed the literature and facilitated the research work; Saad Aziz helped with lab facilities and critical revision of the manuscript. All authors shared equally the revision of the final version.

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Correspondence to Shaaban A. Elroby or Bashair Abdullah Banaser.

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Elroby, S.A., Banaser, B.A., Aziz, S.G. et al. Zn2+-Schiff’s Base Complex as an “On–Off-On” Molecular Switch and a Fluorescence Probe for Cu2+ and Ag+ Ions. J Fluoresc 32, 691–705 (2022). https://doi.org/10.1007/s10895-021-02864-4

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