Theoretical investigation of the stability, reactivity, and the interaction of methyl-substituted peridinium-based ionic liquids

Emmanuel A. Bisong; Hitler Louis; Tomsmith O. Unimuke; Victoria M. Bassey; John A. Agwupuye; Linda I. Peter; Francis O. Ekpen; Aderemi T. Adeleye

doi:10.1515/psr-2020-0137

Article

Theoretical investigation of the stability, reactivity, and the interaction of methyl-substituted peridinium-based ionic liquids

Emmanuel A. Bisong , Hitler Louis , Tomsmith O. Unimuke , Victoria M. Bassey , John A. Agwupuye , Linda I. Peter , Francis O. Ekpen and Aderemi T. Adeleye

Published/Copyright: June 16, 2021

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From the journal Physical Sciences Reviews Volume 8 Issue 8

Abstract

This research work focuses on the reactivity, stability, and electronic interaction of pyridinium hydrogen nitrate (PHN)-based ionic liquids and the influence of methyl substituent on this class of ionic liquids: Ortho- (O-MPHN), meta- (M-MPHN), and para- (P-MPHN) substitution. Natural bond orbital (NBO) calculations were performed at the density functional theory (DFT) with Becke’s Lee Yang and Parr functional (B3LYP) methods and DFT/B3LYP/6-311++G(d,p) as basis set using GAUSSIAN 09W and GAUSSVIEW 6.0 software and the most important interaction between donor (Filled Lewis-type NBO’s) and the acceptor (vacant non-Lewis NBOs) were observed. From our natural bond orbital (NBO) result, it could be deduced that the higher the stabilization energy value, the greater the interaction between the donor and acceptor NBOs. The stability of the studied compounds is said to follow the order from O-MPHN > PHN > P-MPHN > M-MPHN based on the hyperconjugative interaction (stabilization energy) of the most significant interaction. The result of the highest occupied molecular orbital (HOMO), shows that PHN has the highest HOMO while the substituted derivatives have similar HOMO values between −7.70 and −7.98 eV thus PHN complex is the best electron donor while the substituted derivatives act as electron acceptors due to the presence of methyl group substituent which is observed to be electron deficient as a result of its withdrawal effect from the aromatic ring. Furthermore, the electron density, real space functions such as energy density and Laplacian of electron density at bond critical point (BCP) of the hydrogen bond interaction of the studied compounds were analyzed using Multifunctional Wavefunction analyzer software version 3.7 and it was observed that the hydrogen at position 6 and oxygen at position 11 (H6–O11) of M-methyl pyridinium nitrate with bond distance of 4.59 (Å) gave binding energy with the strongest electrostatic interaction between the cation and anion of the compounds under investigation. We also observed from our results that, substitution at the ortho position enhances the stability and strengthen the extent of charge transfer. This therefore implies that substitution at ortho position is more favorable for inter- and intramolecular interactions resulting to stabilization of the studied molecules.

Keywords: DFT; ionic liquids; NBO; nitrate; pyridine; reactivity

Corresponding authors: Emmanuel A. Bisong and Hitler Louis, Department of Pure and Applied Chemistry, Computational and Bio-Simulation Research Group, Faculty of Physical Sciences, University of Calabar, Calabar, Cross River State, Nigeria, E-mail: bisongea@unical.edu.ng (E.A. Bisong), louismuzong@gmail.ocm (H. Louis)

Acknowledgments

This research work was not funded by any external organization. However, Dr. Emmanuel A. Bisong and his coauthors are thankful to computation science research group, University of Calabar, Nigeria headed by Dr. Hitler Louis.

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: None declared.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

References

1. Rajni, R. Ionic liquid synthesis and application in catalysis. Adv Chem 2014;729842:1–16.Search in Google Scholar

2. Patricia, AH, Claire, RA, Richad, PM. Hydrogen bonding in ionic liquids. Chem Soc Rev 2015;44:1257–88. https://doi.org/10.1039/c4c50028d.Search in Google Scholar

3. Ogomi, Y, Kato, T, Hayase, S. Dye sensitized solar cells consisting of ionic liquid and solidification. J Photopolym Sci Technol 2006;19:403–8. https://doi.org/10.2494/photopolymer.19.403.Search in Google Scholar

4. Gorlov, M, Kloo, L. Ionic liquid electrolytes for dye-synthesized solar cells. Dalton Trans 2008;28:2655–66. https://doi.org/10.1039/b716419j.Search in Google Scholar PubMed

5. Irina, VF, Lyubov, PS. The nature of the interactions in triethanolamonium-based Ionic liquids. A quantum chemical study. J Phys Chem A 2018;122:4562–70. https://doi.org/10.1021/acs.jpca.8b02598.Search in Google Scholar PubMed

6. Alessandrini, F, Appetechi, GB, Conte, M, Passen, S. Ionic liquid based electrolytes for high energy electrochemical storage devices. ECS Trans 2006;1:67–71.10.1149/1.2214612Search in Google Scholar

7. Wikes, JS, Zaworotko, M. Air and water stable 1-ethyl-3-methylimidazolium based ionic liquids. J Chem Soc Chem Commun 1992;13:965–7. https://doi.org/10.1039/C39920000965.Search in Google Scholar

8. Dupont, J, de Souza, RF, Suarez, PA. Ionic liquids (molten salt) phase organometallic catalysis. Z Chem Rev 2002;102:3667–92. https://doi.org/10.1021/cr010338r.Search in Google Scholar PubMed

9. Welton, T. Ionic liquids: a brief history. Biophys Rev 2002;10:691–706. https://doi.org/10.1007/s12551-018-0419-2.Search in Google Scholar PubMed PubMed Central

10. Earle, M Ionic liquids in synthesis (Wasserebeid, P, Weston, T, editors.), vol 2. Weinheim: Willey-Vett; 2008. p. 292–369.Search in Google Scholar

11. Ivaylo, T, Rumyana, Y, Svetlana, G, Magdalena, M, Dicho, S. Density functional theory study on the ionic liquids pyridinium hydrogen sulfate. J Mol Struct 2017;1139:400–6.10.1016/j.molstruc.2017.03.040Search in Google Scholar

12. Frisch, MJ, Trucks, GW, Schlegel, HB, Scuseria, GE, Robb, MA, Cheeseman, JR, et al.. Gaussian 09, Revision C. 02. Wallingford CT: Gaussian, Inc.; 2009.Search in Google Scholar

13. Dennington, RD, Keith, TA, Millam, JM. GaussView 6.0. 16, Semichem. Inc., Shawnee Mission KS; 2016.Search in Google Scholar

14. Glenedeming, ED, Reed, AE, Carpenter, JE, Weinhold, F. NBO version 3.1. TCL-University Wis consin Madison; 1998.Search in Google Scholar

15. Lu, T. Multiwfn manual, version 3.7(dev), Section 3.21.1. Available at: http://sobereva.com/multiwfn [Accessed 20 Nov 2019].Search in Google Scholar

16. Theivarasu, C, Murugesan, R. Natural bond orbital (NBO) population analysis of an energetic molecule 1-phenyl-2-nitroguanidine. Int J Chem Sci 2016;14:2029–50.Search in Google Scholar

17. Magdaline, JD, Chithambarathanu, T. Vibrational spectra (FT-IR, FT-Raman), NBO and HOMO, LUMO studies of 2-thiophene carboxylic acid based on density functional method. IOSR J Appl Chem 2015;8:06–14.10.1016/j.matpr.2015.06.021Search in Google Scholar

18. Bisong, EA, Louis, H, Unimuke, TO, Odey, JO, Ubana, EI, Edim, MM, et al.. Vibrational, electronic, spectroscopic, properties and NBO analysis of p-xylene, 3,6-diflouro-p-xylene, 3,6-dichloro-p-xylene, 3,6-dibromo-p-xylene: DFT study. Heliyon 2020;6:e05783. https://doi.org/10.1016/j.heliyon.2020.e05783.Search in Google Scholar PubMed PubMed Central

19. De Lile, JR, Kang, SG, Son, Y-A, Lee, SG. Do HOMO–LUMO energy levels and band gaps provide sufficient understanding of dye-sensitizer activity trends for water purification. ACS Omega 2020.10.1021/acsomega.0c00870Search in Google Scholar

20. Edim, MM, Enudi, OC, Asuquo, BB, Louis, H, Bisong, EA, Agwupuye, JA, et al.. Aromaticity indices, electronic structural properties and fuzzy atomic space investigations of naphthalene and its azo derivatives. Heliyon 2021;7:e06138. https://doi.org/10.1016/j.heliyon.2021.e06138.Search in Google Scholar PubMed PubMed Central

21. Ali, M, Mansha, A, Asim, S, Zahid, M, Usman, M, Ali, N. DFT study for the spectroscopic and structural analysis of p-dimethylaminoazobenzene. J Spectrosc 2018:15.10.1155/2018/9365153Search in Google Scholar

22. Abbaz, T, Amel, B, Villemin, D. Density functional theory studies on molecular structure and electronic properties of sulfanilamide, sulfathiazole, E7070 and furosemide molecules. J Appl Chem 2019;12:60–9.Search in Google Scholar

23. Magdalene, JD, Cjithambarathanu, T. Vibrational spectra (FT-IR, FT-Raman), NBO and HOMO, LUMO studies of 2-thiophene carboxylic acid based on density functional method. J Appl Chem 2015;8:06–14.Search in Google Scholar

24. Lu, T, Chen, F. Atomic dipole moment corrected Hirshfeld population method. J Theor Comput Chem 2012;11:163. https://doi.org/10.1142/s0219633612500113.Search in Google Scholar

25. Liu, Z, Lu, T, Chen, Q. An sp-hybridized all-carboatomic ring, cyclo[18]carbon: bonding character, electron delocalization, and aromaticity. Carbon 2020;165:468–75. https://doi.org/10.1016/j.carbon.2020.04.099.Search in Google Scholar

26. Emamian, S, Lu, T, Kruse, H, Emamian, H. Exploring nature and predicting strength of hydrogen bonds: a correlation analysis between atoms‐in‐molecules descriptors, binding energies, and energy components of symmetry‐adapted perturbation theory. J Comput Chem 2019;40:2868–81. https://doi.org/10.1002/jcc.26068.Search in Google Scholar PubMed

27. Singh, I, El-Emam, A, Pathak, S, Srivastava, R, Shukla, V, Prasad, O, et al.. Experimental and theoretical DFT (B3LYP, X3LYP, CAM-B3LYP and M06-2X) study on electronic structure, spectral features, hydrogen bonding and solvent effects of 4-methylthiadiazole-5-carboxylic acid. Mol Simulat 2019;45:1029–43. https://doi.org/10.1080/08927022.2019.1629434.Search in Google Scholar

28. Arunan, E, Desiraju Gautam, R, Klein Roger, A, Sadlej, J, Scheiner, S, Alkorta, I, et al.. Definition of the hydrogen bond (IUPAC Recommendations 2011). Pure Appl Chem 2011;83:1637–41. https://doi.org/10.1351/pac-rec-10-01-02.Search in Google Scholar

Published Online: 2021-06-16

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Keywords for this article

DFT; ionic liquids; NBO; nitrate; pyridine; reactivity