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Synthesis, physicochemical characterization, and TD–DFT calculations of monothiocarbohydrazone derivatives

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Abstract

Derivatives of thiocarbohydrazone studied so far have shown great biological activity such as antioxidant, antimicrobial, and anticancer. Most of these compounds are bis-substituted derivatives, while monothiocarbohydrazones are much less investigated. Еighteen monothiocarbohydrazones were synthesized and subjected to physicochemical characterization in order to facilitate the examination of their potential biological activity and application in future studies. The structure of synthesized derivatives was confirmed with NMR and FT–IR spectroscopy, and with elemental analysis. For one of the compounds, single-crystal X-ray diffraction analysis was performed. Specific and non-specific molecular interactions were interpreted by LSER principles, using Catalan’s model. For additional information about the dominance and influence of the interactions presented, correlations with Hansen’s solubility parameters were calculated. Influence of the type and position of the substituent on absorption maxima was determined with LFER (linear free-energy relationship) principles, using Hammett’s equation. Acidity constants of the synthesized compounds were theoretically calculated and experimentally determined. Moreover, the excitation of a molecule by a photon of UV–Vis light was interpreted by time-dependent density functional theory (TD–DFT) calculations of UV absorption bands, and intramolecular charge transfer (ICT) was quantified by calculations of the charge transfer distances (DCT).

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Data availability

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

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Funding

The authors acknowledge financial support of the Ministry of Education, Science and Technological Development of the Republic of Serbia (Grants No. 451-03-68/2020-14/ 200125; 451-03-68/2020-14/200026; 451-03-68/2020-14/200168).

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Authors and Affiliations

  1. Faculty of Sciences, University of Novi Sad, Trg Dositeja Obradovića 3, Novi Sad, 21000, Serbia

    Gorana S. Mrđan, Gyöngyi Gy. Vastag, Dušan Đ. Škorić, Mirjana M. Radanović & Borko M. Matijević

  2. Faculty of Chemistry, University of Belgrade, Studentski trg 12–16, Belgrade, 11000, Serbia

    Tatjana Ž. Verbić & Miloš K. Milčić

  3. Faculty of Forestry, University of Belgrade, Kneza Višeslava 1, Belgrade, 11000, Serbia

    Ivana N. Stojiljković

  4. Department of Chemistry, Institute of Chemistry, Technology and Metallurgy – National Institute of the Republic of Serbia, University of Belgrade, Njegoševa 12, Belgrade, 11000, Serbia

    Olivera S. Marković

Authors
  1. Gorana S. Mrđan
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  2. Gyöngyi Gy. Vastag
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  3. Dušan Đ. Škorić
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  4. Mirjana M. Radanović
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  5. Tatjana Ž. Verbić
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  6. Miloš K. Milčić
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  7. Ivana N. Stojiljković
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  8. Olivera S. Marković
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  9. Borko M. Matijević
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Contributions

All authors contributed to the study conception and design. Material preparation, data collection, and synthesis of the compounds were performed by G. Mrdjan. Structural characterization, X-ray analysis, and interpretation of the specific and non-specific interactions were performed and analyzed by G. Mrdjan, D. Škorić, M. Radanović, Gy. Vastag, and B. Matijević. Determination of the pKa was performed by T. Verbić, and O. Marković. TD–DFT calculations were carried out by M. Milčić, and I. Stojiljković. The first draft of the manuscript was written by G. Mrdjan, and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

Corresponding author

Correspondence to Gorana S. Mrđan.

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Mrđan, G.S., Vastag, G.G., Škorić, D.Đ. et al. Synthesis, physicochemical characterization, and TD–DFT calculations of monothiocarbohydrazone derivatives. Struct Chem 32, 1231–1245 (2021). https://doi.org/10.1007/s11224-020-01700-y

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