Skip to main content

Advertisement

SpringerLink
Log in

TD-DFT investigation on anion recognition mechanism of anthraldehyde-based fluorescent thiosemicarbazone derivatives

  • Original Paper
  • Published:
Journal of Molecular Modeling Aims and scope Submit manuscript

Abstract

The mechanism of host–guest interaction of receptors towards fluoride ion has been investigated using computational methods. To distinguish the effect of aromaticity in host–guest interaction, we investigated unsubstituted (ATSC) and phenyl-substituted (APTSC) anthracene thiosemicarbazones towards different ions. In the ground state of receptor-fluoride complex, the added fluoride ion made hydrogen bond through N − H…F…H − N, whereas the intramolecular hydrogen bonding was through F − H…N in the excited state of receptor-fluoride complex. Experimental absorption and emission spectra were well reproduced by the calculated vertical excitation energies. The transition state (TS) calculations were performed to understand the thermodynamic features and mechanism of host–guest interaction. The natural bond orbital analyses show that the second perturbation energy for donor–acceptor interaction of F− with hydrogen is more than 300 kcal/mol−1 at the excited state of receptor-fluoride complex, which indicates the strong single bond between fluoride and hydrogen atom. The PES scan confirms that deprotonation took place at the excited state of receptor-fluoride complex. The results indicate the excited-state proton transfer (ESPT) process from N–H group nearby the anthracene moiety. The APTSC is a better chemosensor than ATSC. This infers that the aromaticity will increase the efficiency of fluorescence receptor towards fluoride ion.

Graphical abstract

A schematic representation of sensing mode of anthracene-based thiosemicarbazones toward fluoride ion. The fluoride ion first makes a hydrogen bond with NH proton nearby anthracene moiety. The excited state proton transfer mechanism was confirmed by PES and NBO studies.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

Data availability

The xyz coordinates of optimised structure of receptor and receptor-fluoride complexes are given in supplementary information.

Code availability

N/A.

References

  1. Jo TG, Na YJ, Lee JJ, Lee MM, Lee SY, C.A. (2015) Kim, A multifunctional colorimetric chemosensor for cyanide and copper(II) ions. Sens. Actuators B 211:498–506

    Article  CAS  Google Scholar 

  2. Chen JS, Zhou PW, Zhaoab L, Chu TS (2014) A DFT/TDDFT study of the excited state intramolecular proton transfer based sensing mechanism for the aqueous fluoride chemosensor BTTPB. RSC Adv 4:254–259

    Article  CAS  Google Scholar 

  3. Carvalho CP, Ferreiraa R, Silva JPD, Pischel U (2013) An aminonaphthalimide–putrescine conjugate as fluorescent probe for cucurbituril host–guest complexes. Supramol Chem 25:92–100

    Article  CAS  Google Scholar 

  4. Li GY, Liu D, Zhang H, Li WW, Wang F, Liang YH (2015) TDDFT study on the sensing mechanism of a fluorescent sensor for fluoride anion: Inhibition of the ESPT process. Spectrochim Acta Mol Biomol Spectrosc 149:17–22

    Article  CAS  Google Scholar 

  5. Harikrishnan VK, Basheer SM, Joseph N, Sreekanth A (2017) Colorimetric and fluorimetric response of salicylaldehyde dithiosemicarbazone towards fluoride, cyanide and copper ions: spectroscopic and TD-DFT studies, spectrochim. Acta Mol Biomol Spectrosc 182:160–167

    Article  CAS  Google Scholar 

  6. Basheer SM, Haribabu J, Bhuvanesh NSP, Karvembu R, Sreekanth A (2017) Naphthalenyl appended semicarbazone as “turn on” fluorescent chemosensor for selective recognition of fluoride ion. J Mol Struct 1145:347–355

    Article  CAS  Google Scholar 

  7. Hasegawa J, Miyazaki R, Maeda C, Ema T (2016) Theoretical study on highly active bifunctional metalloporphyrin catalysts for the coupling reaction of epoxides with carbon dioxide. Chem Rec 16:2260–2267

    Article  CAS  Google Scholar 

  8. Rezaeian K, Khanmohammadi H (2016) Molecular logic circuits and a security keypad lock based on a novel colorimetric azo receptor with dual detection ability for copper(II) and fluoride ions. Supramol. Chem 28:256–266

    Article  CAS  Google Scholar 

  9. Zhu B, Kan LH, Liu H, Wei Q, Du B (2014) A highly selective ratiometric visual and red-emitting fluorescent dual-channel probe for imaging fluoride anions in living cells. Biosens Bioelectron 52:298–303

    Article  CAS  Google Scholar 

  10. Su Y, Chai S (2014) A TDDFT study of the excited-state intramolecular proton transfer of 1,3-bis(2-pyridylimino)-4,7-dihydroxyisoindole. J Photochem Photobiol A 290:109–115

    Article  CAS  Google Scholar 

  11. Basheer SM, Willis AC, Pace RJ, Sreekanth A (2016) Spectroscopic and TD-DFT studies on the turn-off fluorescent chemosensor based on anthraldehyde N(4) cyclohexyl thiosemicarbazone for the selective recognition of fluoride and copper ions. Polyhedron 109:7–18

    Article  CAS  Google Scholar 

  12. Duke RM, O’Brien JE, McCabe T, Gunnlaugsson T (2008) Colorimetric sensing of anions in aqueous solution using a charge neutral, cleft-like, amidothiourea receptor: tilting the balance between hydrogen bonding and deprotonation in anion recognition. Org Biomol Chem 6:4089–4092

    Article  CAS  Google Scholar 

  13. Basheer SM, Muralisankar M, Anjana TV, Aneesrahman KN, Sreekanth A (2017) Multi-ion detection and molecular switching behaviour of reversible dual fluorescent sensor. Spectrochim Acta Mol Biomol Spectrosc 182:95–104

    Article  CAS  Google Scholar 

  14. Jin R, Sun W, Tang S (2012) A DFT study of pyrrole-isoxazole derivatives as chemosensors for fluoride anion. Int J Mol Sci 13:10986–10999

    Article  CAS  Google Scholar 

  15. Jin R, Irfan A (2012) Theoretical study of coumarin derivatives as chemosensors for fluoride anion. Comp Theor Chem 986:93–98

    Article  CAS  Google Scholar 

  16. Detert H, Lehmann M, Meier H (2010) Star-shaped conjugated systems Materials 3:3218–3330

    CAS  Google Scholar 

  17. R.X. He, X.Y. Li, An anti-quinoid structure in dual fluorescence of fluozazene molecule and solvent effect of intramolecular charge transfer. Chem. Phys.http://www.sciencedirect.com/science/journal/03010104/332/2 (2007) 32S5–335.

  18. Basheer SM, Kumar SLA, Kumar MS, Sreekanth A (2017) Spectroscopic and TDDFT investigation on highly selective fluorogenic chemosensor and construction of molecular logic gates. Mater Sci Eng C 72:667–675

    Article  CAS  Google Scholar 

  19. Bozdemir OA, Guliyev R, Buyukcakir O, Selcuk S, Kolemen S, Gulseren G, Nalbantoglu T, Boyaci H, Akkaya EU (2010) Selective manipulation of ICT and PET processes in styryl-bodipy derivatives: applications in molecular logic and fluorescence sensing of metal ions. J Am Chem Soc 132:8029–8036

    Article  CAS  Google Scholar 

  20. Basheer SM, Bhuvanesh NSP, Sreekanth A (2016) Experimental and theoretical studies of novel hydroxynaphthalene based chemosensor, and construction of molecular logic gates. J Fluorine Chem 191:129–142

    Article  CAS  Google Scholar 

  21. Basheer SM, Willis AC, Sreekanth A (2017) Spectroscopic and TD-DFT studies on the dual mode fluorescent chemosensors based on pyrene thiosemicarbazones, and its application as molecular-scale logic devices. J Lumin 183:266–280

    Article  CAS  Google Scholar 

  22. Rosal ID, Poteaua R, Maron L (2011) DFT study of the ring opening polymerization of ε-caprolactone by grafted lanthanide complexes: effect of the grafting mode on the reactivity of borohydride complexes. Dalton Trans 40:11211–11227

    Article  Google Scholar 

  23. Udayakumari D, Velmathi S, Venkatesan P, Wo SP (2015) Anthracene coupled thiourea as a colorimetric sensor for F-/Cu2+ and fluorescent sensor for Hg2+ picric acid. J Lumin 161:411–416

    Article  Google Scholar 

  24. Yanai T, Tew DP, Handy NC (2004) A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP). Chem Phys Lett 393:51–57

    Article  CAS  Google Scholar 

  25. Pir H, Günay N, Avc D, Atalay Y (2012) Molecular structure, vibrational spectra, NLO and NBO analysis of bis (8-oxy-1-methyl quinolinium) hydroiodide. Spectrochim Acta Mol Biomol Spectrosc 96:916–924

    Article  CAS  Google Scholar 

  26. Guha S, Saha S (2010) Fluoride ion sensing by an anion-π interaction. J Am Chem Soc 132:17674–17677

    Article  CAS  Google Scholar 

  27. Basheer SM, Sreekanth A (2016) TD-DFT study on the fluoride and copper ion sensing mechanism of pyrene N(4) phenyl thiosemicarbazone. Comp Theor Chem 1085:31–39

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Author SMB is grateful to the RGEMS, VIT-AP University, Andhra Pradesh, India, for the financial support.

Author information

Authors and Affiliations

  1. Department of Chemistry, School of Advanced Sciences, VIT-AP University, Andhra Pradesh, Amaravati, India, 522 237

    Sabeel M. Basheer

  2. Department of Chemistry, National Institute of Technology-Tiruchirappalli, Tiruchirappalli-620015, Tamil Nadu, India

    Rohini Gandhaveeti

Authors
  1. Sabeel M. Basheer
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Rohini Gandhaveeti
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Dr. SMB conceived and designed the computational analysis and wrote the paper; however, Dr. RG contributed in data and analysis tools.

Corresponding author

Correspondence to Sabeel M. Basheer.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Additional information

Publisher's note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOCX 16 KB)

Rights and permissions

Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Basheer, S.M., Gandhaveeti, R. TD-DFT investigation on anion recognition mechanism of anthraldehyde-based fluorescent thiosemicarbazone derivatives. J Mol Model 28, 234 (2022). https://doi.org/10.1007/s00894-022-05235-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00894-022-05235-3

Keywords

Search

Navigation