Exploring Noncovalent Interactions of Thiophene-2-Car¬boxylic Acid in Ethanol Via Vibrational Spectroscopy and DFT Calculations
DOI:
https://doi.org/10.15407/ujpe70.6.391Keywords:
vibrational spectroscopy, DFT calculation, intermolecular interaction, topological parametersAbstract
The spectral bands of pure 2-thiophene carboxylic acid (TCA) and its solution in ethanol (EtOH) are investigated over a wide range using vibrational spectroscopy (Raman and FTIR). In the TCA solution with EtOH, the maxima of the C=O, O–H, C–H stretching, and C–H breathing vibration bands show either a redshift or a blueshift. This indicates that H-bonding, van der Waals interactions, and hyper-conjugation interactions are likely in solutions. MEPS, HOMO and LUMO, AIM, NCI, RDG, ELF, and LOL analyses are performed using a quantum chemical computational approach based on density functional theory (DFT). The MEPS map was used to visually show the charge distribution in the complexes and determine charge-dependent characteristics. Frontier molecular orbitals (FMO) have been utilized to explain chemical reactivity of TCA, its molecular stability, as well as electrical and optical properties. According to AIM, NCI, and RDG analysis, TCA and TCA-EtOH complexes mainly have moderate H-bonding.
References
1. F. Cagnin, E.E. Castellano, M.R. Davolos. Synthesis and structural characterization of a new polymeric zinc(II) complex with thiophene-2-carboxylic acid. J. Coord. Chem. 63, 2278 (2010).
https://doi.org/10.1080/00958972.2010.503271
2. V. Hern'andez, F.J. Ram'ırez, J. Casado, F. Enr'ıquez, J.J. Quirante, J.L. Navarrete. Ab initio RHF 6-31G** theoretical study of thiophene derivatives: 2-methylthiophene and 3-methylthiophene. J. Mol. Struct. 410, 311 (1997).
https://doi.org/10.1016/S0022-2860(96)09469-0
3. T. Kupka, R. Wrzalik, G. Pasterna, K. Pasterny. Theoretical DFT and experimental Raman and NMR studies on thiophene, 3-methylthiophene, and selenophene. J. Mol. Struct. 616, 17 (2002).
https://doi.org/10.1016/S0022-2860(02)00177-1
4. T. Karthick, V. Balachandran, S. Perumal. Spectroscopic investigations, molecular interactions, and molecular docking studies on the potential inhibitor "thiophene-2-carboxylic acid". Spectrochim. Acta A Mol. Biomol. Spectrosc. 141, 104 (2015).
https://doi.org/10.1016/j.saa.2015.01.025
5. G.D. Fleming, R. Koch, M.C. Vallete. Theoretical study of the syn and anti thiophene-2-aldehyde conformers using density functional theory and normal coordinate analysis. Spectrochim. Acta A Mol. Biomol. Spectrosc. 65, 935 (2006).
https://doi.org/10.1016/j.saa.2006.01.038
6. V. Balachandran, A. Janaki, A. Nataraj. Theoretical investigations on molecular structure, vibrational spectra, HOMO, LUMO, NBO analysis, and hyperpolarizability calculations of thiophene-2-carbohydrazide. Spectrochim. Acta A Mol. Biomol. Spectrosc. 118, 321 (2014).
https://doi.org/10.1016/j.saa.2013.08.091
7. L.L. Gladkov, S.V. Gaponenko, E.V. Shabunya-Klyachkovskaya, A.N. Shimko, E.S. Al-Abdullah, A.A. ElEmam. Vibrational spectroscopy of N′-(adamantan-2-ylidene) thiophene-2-carbohydrazide, a potential antibacterial agent. Spectrochim. Acta Part A Mol. Biomol. Spectrosc. 128, 874 (2014).
https://doi.org/10.1016/j.saa.2014.02.071
8. S. Abbas, M. Hussain, S. Ali, M. Parvez, A. Raza, A. Haider, J. Iqbal. Structural, enzyme inhibition, antibacterial and DNA protection studies of organotin (IV) derivatives of thiophene-2-carboxylic acid. J. Organomet. Chem. 724, 255 (2013).
https://doi.org/10.1016/j.jorganchem.2012.11.033
9. T. Nasr, S. Bondock, S. Eid. Design, synthesis, antimicrobial evaluation and molecular docking studies of some new thiophene, pyrazole and pyridone derivatives bearing sulfisoxazole moiety. Eur. J. Med. Chem. 84, 491 (2014).
https://doi.org/10.1016/j.ejmech.2014.07.052
10. P.K. Sarswat, A. Sathyapalan, Y. Zhu, M.L. Free. Design, synthesis, and characterization of TPA-thiophenebased amide or imine functionalized molecule for potential optoelectronic devices. J. Theor. Appl. Phys. 7, 1 (2013).
https://doi.org/10.1186/2251-7235-7-4
11. U.K. Sarkar. A pH-dependent SERS study of thiophene-2-carboxylic acid adsorbed on Ag-sols. Chem. Phys. Lett. 374, 341 (2003).
https://doi.org/10.1016/S0009-2614(03)00728-0
12. A. Jumabaev, H. Hushvaktov, B. Khudaykulov, A. Absanov, M. Onuk, I. Doroshenko, L. Bulavin. Formation of hydrogen bonds and vibrational processes in dimethyl sulfoxide and its aqueous solutions: Raman spectroscopy and ab initio calculations. Ukr. J. Phys. 68, 375 (2023).
https://doi.org/10.15407/ujpe68.6.375
13. A. Jumabaev, S.J. Koyambo-Konzapa, H. Hushvaktov et al. Intermolecular interactions in water and ethanol solution of ethyl acetate: Raman, DFT, MEP, FMO, AIM, NCI-RDG, ELF, and LOL analyses, J. Mol. Model. 30, 349 (2024).
https://doi.org/10.1007/s00894-024-06147-0
14. J.G. Moberly, M.T. Bernards, K.V. Waynant. Key features and updates for Origin 2018. J Cheminform 10, 5 (2018).
https://doi.org/10.1186/s13321-018-0259-x
15. M.J. Frisch et al. Gaussian 09, Revision D.1, Gaussian Inc., Wallingford, 2009.
16. J. Zhang, M. Dolg. ABCluster: The artificial bee colony algorithm for cluster global optimization. Phys. Chem. Chem. Phys. 17, 24173 (2015).
https://doi.org/10.1039/C5CP04060D
17. A.D. Becke. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648 (1993).
https://doi.org/10.1063/1.464913
18. C. Lee, W. Yang, R.G. Parr. Development of the Colle-Salvetti correlation energy formula into a functional of the electron density. Phys. Rev. B Condens. Matter. 37, 785 (1998).
https://doi.org/10.1103/PhysRevB.37.785
19. T. Lu, F. Chen. Multiwfn: A multifunctional wavefunction analyzer. J. Comput. Chem. 33, 580 (2012).
https://doi.org/10.1002/jcc.22885
20. W. Humphrey, A. Dalke, K. Schulten. VMD: Visual molecular dynamics. J. Mol. Graph. 14, 33 (1996).
https://doi.org/10.1016/0263-7855(96)00018-5
21. A. Jumabaev, B. Khudaykulov, I. Doroshenko, H. Hushvaktov, A. Absanov. Raman and ab initio study of intermolecular interactions in aniline. Vib. Spectrosc. 122, 103422 (2022).
https://doi.org/10.1016/j.vibspec.2022.103422
22. H. Hushvaktov, B. Khudaykulov, A. Jumabaev, I. Doroshenko, A. Absanov, G. Murodov. Study of formamide molecular clusters by Raman spectroscopy and quantumchemical calculations. Mol. Cryst. Liq. Cryst. 749, 124 (2022).
https://doi.org/10.1080/15421406.2022.2068478
23. O. Mishchuk, I. Doroshenko, V. Sablinskas, V. Balevicius. Temperature evolution of cluster structure in n-hexanol, isolated in Ar and N2 matrices and in condensed states. Struct. Chem. 27, 243 (2016).
https://doi.org/10.1007/s11224-015-0692-7
24. H. Hushvaktov, F. Tukhvatullin, A. Jumabaev, U. Tashkenbaev, A. Absanov, B. Hudoyberdiev, B. Kuyliev. Raman spectra and ab initio calculation of a structure of aqueous solutions of methanol. J. Mol. Struct. 1131, 25 (2017).
https://doi.org/10.1016/j.molstruc.2016.10.061
25. G.A. Pitsevich, I.Yu. Doroshenko, V.Ye. Pogorelov, E.N. Kozlovskaya, T. Borzda, V. Sablinskas, V. Balevicius. Long-wave Raman spectra of some normal alcohols. Vibr. Spectrosc. 72, 26 (2014).
https://doi.org/10.1016/j.vibspec.2014.02.003
26. V. Balevicius, V. Sablinskas, I. Doroshenko, V. Pogorelov. Propanol clustering in argon matrix: 2D FTIR correlation spectroscopy. Ukr. J. Phys. 56, 855 (2011).
https://doi.org/10.15407/ujpe56.8.855
27. I. Doroshenko, V. Pogorelov, V. Sablinskas, V. Balevicius. Matrix-isolation study of cluster formation in methanol: O-H stretching region. J. Mol. Liq. 157, 142 (2010).
https://doi.org/10.1016/j.molliq.2010.09.003
28. E. Mrazkova, P. Hobza. Hydration of sulfo and methyl groups in dimethyl sulfoxide is accompanied by the formation of red-shifted hydrogen bonds and improper blueshifted hydrogen bonds: An ab initio quantum chemical study. J. Phys. Chem. A 107, 1032 (2003).
https://doi.org/10.1021/jp026895e
29. M. Lu, H. Haoran, W. Congmin, X. Yingjie, H. Shijun. Prediction of vapor-liquid equilibria data from C-H band shifts of Raman spectra and activity coefficients at infinite dilution in some aqueous systems. Ind. Eng. Chem. Res. 44, 6883 (2005).
https://doi.org/10.1021/ie050078u
30. T. Lu, F. Chen. Quantitative analysis of molecular surface based on improved marching tetrahedra algorithm. J. Mol. Graph. Model. 38, 314 (2012).
https://doi.org/10.1016/j.jmgm.2012.07.004
31. A. Jumabaev, H. Hushvaktov, A. Absanov, B. Khudaykulov, Z. Ernazarov, L. Bulavin. Vibrational spectra and computational study of amyl acetate: MEP, AIM, RDG, NCI, ELF and LOL analysis. Ukr. J. Phys. 69, 742 (2024).
https://doi.org/10.15407/ujpe69.10.742
32. A. Jumabaev, U. Holikulov, H. Hushvaktov, A. Absanov, L. Bulavin. Interaction of valine with water molecules: Raman and DFT study. Ukr. J. Phys. 67, 602 (2022).
https://doi.org/10.15407/ujpe67.8.602
33. U. Holikulov, A.S. Kazachenko, N. Issaoui, A.S. Kazachenko, M. Raja, O.M. Al-Dossary, Z. Xiang. The molecular structure, vibrational spectra, solvation effect, non-covalent interactions investigations of psilocin. Spectrochim. Acta Part A: Mol. Biomol. Spectrosc. 320, 124600 (2024).
https://doi.org/10.1016/j.saa.2024.124600
34. A.S. Kazachenko, N. Issaoui, U. Holikulov, O.M. AlDossary, I.S. Ponomarev, A.S. Kazachenko, F. Akman, L.G. Bousiakou. Noncovalent interactions in N-methylurea crystalline hydrates. Z. Phys. Chem. 238, 89 (2024).
https://doi.org/10.1515/zpch-2023-0345
35. J.-L. Bredas. Mind the gap! Mater. Horiz. 1, 17 (2014).
https://doi.org/10.1039/C3MH00098B
36. A.S. Kazachenko, U. Holikulov, N. Issaoui, O.M. AlDossary, I.S. Ponomarev, A.S. Kazachenko, F. Akman, L.G. Bousiakou. Theoretical and experimental approach on investigation of ethylurea-water clusters. Z. Phys. Chem. 238, 683 (2024).
https://doi.org/10.1515/zpch-2023-0381
37. R.F.W. Bader. Definition of molecular structure: By choice or by appeal to observation? J. Phys. Chem. A 114, 7431 (2010).
https://doi.org/10.1021/jp102748b
38. I. Rozas, I. Alkorta, J. Elguero. Behavior of ylides containing N, O, and C atoms as hydrogen bond acceptors. Am. Chem. Soc. 122, 11154 (2000).
https://doi.org/10.1021/ja0017864
39. T.-H. Tang, E. Deretey, S.J. Knak Jensen, I.G. Csizmadia. Hydrogen bonds: Relation between lengths and electron densities at bond critical points. Eur. Phys. J. D 37, 217 (2006).
https://doi.org/10.1140/epjd/e2005-00317-0
40. A. Jumabaev, H. Hushvaktov, A. Absanov, I. Doroshenko, B. Khudaykulov. Experimental and computational analysis of C≡ N and C-H stretching bands in acetonitrile solutions. Low Temp. Phys. 51, 202 (2025).
https://doi.org/10.1063/10.0035404
41. K. Arulaabaranam, G. Mani, S. Muthu. Computational assessment on wave function (ELF, LOL) analysis, molecular confirmation and molecular docking explores on 2-(5-Amino-2-Methylanilino)-4-(3-pyridyl) pyrimidine. Chem. Data Collect. 29, 100525 (2020).
https://doi.org/10.1016/j.cdc.2020.100525
42. Y. Li, M. Lin, M. Tian, G. Ye, X. Zhao. DFT computational and spectroscopic studies on andrographolide from different solvent effects. J. Mol. Liq. 390, 123059 (2023).
https://doi.org/10.1016/j.molliq.2023.123059
43. A. Jumabaev, B. Khudaykulov, U. Holikulov, A. Norkulov, J. Subbiah, O. Al-Dossary, H. Hushvaktov, A. Absanov, N. Issaoui. Molecular structure, vibrational spectral assignments, MEP, HOMO-LUMO, AIM, NCI, RDG, ELF, LOL properties of acetophenone and for its solutions based on DFT calculations. Opt. Mater. 159, 116683 (2025).
https://doi.org/10.1016/j.optmat.2025.116683
44. B. Khudaykulov, A. Norkulov, U. Holikulov, A. Absanov, I. Doroshenko, A. Jumabaev. Raman and DFT study of non-covalent interactions in liquid benzophenone and its solutions. Low Temp. Phys. 51, 220 (2025).
Downloads
Published
Issue
Section
License
Copyright Agreement
License to Publish the Paper
Kyiv, Ukraine
The corresponding author and the co-authors (hereon referred to as the Author(s)) of the paper being submitted to the Ukrainian Journal of Physics (hereon referred to as the Paper) from one side and the Bogolyubov Institute for Theoretical Physics, National Academy of Sciences of Ukraine, represented by its Director (hereon referred to as the Publisher) from the other side have come to the following Agreement:
1. Subject of the Agreement.
The Author(s) grant(s) the Publisher the free non-exclusive right to use the Paper (of scientific, technical, or any other content) according to the terms and conditions defined by this Agreement.
2. The ways of using the Paper.
2.1. The Author(s) grant(s) the Publisher the right to use the Paper as follows.
2.1.1. To publish the Paper in the Ukrainian Journal of Physics (hereon referred to as the Journal) in original language and translated into English (the copy of the Paper approved by the Author(s) and the Publisher and accepted for publication is a constitutive part of this License Agreement).
2.1.2. To edit, adapt, and correct the Paper by approval of the Author(s).
2.1.3. To translate the Paper in the case when the Paper is written in a language different from that adopted in the Journal.
2.2. If the Author(s) has(ve) an intent to use the Paper in any other way, e.g., to publish the translated version of the Paper (except for the case defined by Section 2.1.3 of this Agreement), to post the full Paper or any its part on the web, to publish the Paper in any other editions, to include the Paper or any its part in other collections, anthologies, encyclopaedias, etc., the Author(s) should get a written permission from the Publisher.
3. License territory.
The Author(s) grant(s) the Publisher the right to use the Paper as regulated by sections 2.1.1–2.1.3 of this Agreement on the territory of Ukraine and to distribute the Paper as indispensable part of the Journal on the territory of Ukraine and other countries by means of subscription, sales, and free transfer to a third party.
4. Duration.
4.1. This Agreement is valid starting from the date of signature and acts for the entire period of the existence of the Journal.
5. Loyalty.
5.1. The Author(s) warrant(s) the Publisher that:
– he/she is the true author (co-author) of the Paper;
– copyright on the Paper was not transferred to any other party;
– the Paper has never been published before and will not be published in any other media before it is published by the Publisher (see also section 2.2);
– the Author(s) do(es) not violate any intellectual property right of other parties. If the Paper includes some materials of other parties, except for citations whose length is regulated by the scientific, informational, or critical character of the Paper, the use of such materials is in compliance with the regulations of the international law and the law of Ukraine.
6. Requisites and signatures of the Parties.
Publisher: Bogolyubov Institute for Theoretical Physics, National Academy of Sciences of Ukraine.
Address: Ukraine, Kyiv, Metrolohichna Str. 14-b.
Author: Electronic signature on behalf and with endorsement of all co-authors.
.png){kind=small}
