Abstract
Experimental and theoretical studies of 2-(2-Nitrovinyl) thiophene were conducted using density functional theory (DFT/B3LYP) at 6-311G basis sets to evaluate molecular geometry, vibrational analysis and electronic absorption spectra. The title compound became characterized through spectroscopic techniques by the usage of FTIR (400–4000 cm−1), FT-Raman (50–4000 cm−1), UV–Visible and NMR spectra both theoretically and experimentally. Several bond parameters, namely bond lengths, bond angles and dihedral angles, were evaluated. The observed HOMO and LUMO energy gaps affirm that the charge transfer happens inside the title compound. Molecular Electrostatic Potential Map, first hyperpolarizability and Fukui functions calculations had been additionally done with the same level of basis set. Several global reactivity descriptors were calculated, and correlation between them as well as the effectiveness of corrosion inhibition could be established. Molecular orbital computational analysis suggests the biologically active properties based on its global reactivity. A study has been conducted to examine the correlation among the structural and optoelectronic properties of the molecules by investigating how electron-donating and electron-withdrawing groups affect the geometry and electronic properties along with the photophysical properties of the molecules. These properties suggest that the title compound is an exquisite candidate for organic solar cells.
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs11696-024-03311-x/MediaObjects/11696_2024_3311_Fig1a_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs11696-024-03311-x/MediaObjects/11696_2024_3311_Fig1b_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs11696-024-03311-x/MediaObjects/11696_2024_3311_Fig2a_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs11696-024-03311-x/MediaObjects/11696_2024_3311_Fig2b_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs11696-024-03311-x/MediaObjects/11696_2024_3311_Fig3a_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs11696-024-03311-x/MediaObjects/11696_2024_3311_Fig3b_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs11696-024-03311-x/MediaObjects/11696_2024_3311_Fig4a_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs11696-024-03311-x/MediaObjects/11696_2024_3311_Fig4b_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs11696-024-03311-x/MediaObjects/11696_2024_3311_Fig5a_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs11696-024-03311-x/MediaObjects/11696_2024_3311_Fig5b_HTML.png)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs11696-024-03311-x/MediaObjects/11696_2024_3311_Fig6_HTML.png)
Similar content being viewed by others
References
Arjunan V, Balamourougane PS, Govindaraja ST, Mohan S (2012) A comparative study on vibrational, conformational and electronic structure of 2-(hydroxymethyl) pyridine and 3-(hydroxymethyl) pyridine. J Mol Struct 1018:156–170. https://doi.org/10.1016/j.molstruc.2012.03.017
Arjunan V, Santhanam R, Rani T, Rosi H, Mohan S (2013) FTIR, FT-Raman, FT-NMR and quantum chemical investigations of 3-acetylcoumarin. Spectrochim Acta Mol Biomol Spectrosc 109:79–89. https://doi.org/10.1016/j.saa.2013.01.100
Ashalatha BV, Narayana B, Raj KKV, Kumari NS (2008) Synthesis of some new bioactive 3-amino-2-mercapto-5,6,7,8-tetrahydro[1]benzothieno[2,3-d]pyrimidin-4(3H)-one derivatives. Euro J Medi Chem 42:719–728. https://doi.org/10.1016/j.ejmech.2006.11.007
Ayers PW, Parr RG (2008) Local hardness equalization: exploiting the ambiguity. J Chem Phys 128:184108. https://doi.org/10.1063/1.2918731
Babu NR, Subashchandrabose S, Padusha MSA, Saleem H, Manivannan V et al (2014) Synthesis and structural characterization of (E)-N′((Pyridin-2-yl) methylene) benzohydrazide by X-ray diffraction, FTIR, FT-Raman and DFT methods. J Mol Struct 1072:84–93
Balachandran V, Janaki A, Nataraj A (2014) Theoretical investigations on molecular structure, vibrational spectra, HOMO, LUMO, NBO analysis and hyperpolarizability calculations of thiophene-2carbohydrazide. Spectrochim Acta A Mol Biomol Spectrosc 118:321–330
Balakit AA, Makki SQ, Sert Y et al (2020) Synthesis, Spectrophotometric and DFT studies of new triazole Schiff bases as selective naked-eye sensors for acetate anion. Supramol Chem 32:519–526. https://doi.org/10.1080/10610278.2020.1808217
Becke AD (1993) Density-functional thermochemistry. III. The role of exact exchange. J Chem Phys 98:5648. https://doi.org/10.1063/1.464913
Bouachrine M, El Alamy A, Amine A, Hamidi M, Bouzzine S (2015) New compounds based on quaterthiophene and benzo [1, 2, 5] thiadiazole for solar cells application: correlation structure/electronic properties. Moroccan J Chem 3(4):3–4. https://doi.org/10.48317/IMIST.PRSM/morjchem-v3i4.3034
Brathen O, Kveseth K, Nielsen CJ, Hagen K (1986) Molecular structure and conformational equilibrium of gaseous thiophene-2-aldehyde as studied by electron diffraction and microwave, infrared, Raman and matrix isolation spectroscopy. J Mol Struct 145:45–68
Camila G, Alexandre F (2014) Corrosion inhibitors—principles, mechanisms and applications. In: Aliofkhazraei M (ed) Developments in Corrosion Protection. InTech. https://doi.org/10.5772/57255
Charanya C, Sampathkrishnan S, Balamurugan N (2020) Quantum chemical computations, molecular docking, experimental and DFT calculation of 4-amino-3- phenylbutanoic acid. Polycycl Aromat Comp. https://doi.org/10.1080/10406638.2020.1776347. (ISSN:1040-6638(Print)1563-5333(Online))
Choong IC, Lew W, Lee D, Pham P, Burdett MT, Lam JW, Wiesmann C, Luong TN, Fahr B, DeLano WL, McDowell RS, Allen DA, Erlanson DA, Gordon EM, O’Brien T (2002) Identification of potent and selective small-molecule inhibitors of caspase-3 through the use of extended tethering and structure-based drug design. J Med Chem 45(23):5005–5022. https://doi.org/10.1021/jm020230j. (PMID: 12408711)
Dhevaraj J, Vembu S, Pazhamalai S, Gopalakrishnan M (2019) Design and synthesis of some cyclic carbohydrates with norfloxacin as surface moiety. A study of sustained relax of drugs. Orient J Chem 35(2):577. https://doi.org/10.13005/ojc/350211
Doré K, Dubus S, Ho HA, Lévesque I, Brunette M, Corbeil G, Leclerc M (2004) Fluorescent polymeric transducer for the rapid, simple, and specific detection of nucleic acids at the zeptomole level. J Am Chem Soc 126(13):4240–4244
Doré K, Dubus S, Ho H-A, Lévesque I, Brunette M, Corbeil G, Boissinot M, Boivin G, Bergeron MG, Boudreau D, Leclerc M (2004) Fluorescent polymeric transducer for the rapid, simple, and specific detection of nucleic acids at the Zeptomole level. J Am Chem Soc 126(13):4240–4244. https://doi.org/10.1021/ja038900d
Fleming GD, Koch R, Vallete MMC (2006) 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 65:935–945
Frisch MJ, Trucks GW, Schlegal HB et al. (2009) GAUSSIAN 09, Revision A.02, Gaussian, Inc., Wallingford CT
Gadisa A, Svensson M, Andersson MR, Inganäs O (2004) Correlation between oxidation potential and open-circuit voltage of composite solar cells based on blends of polythiophenes/fullerene derivative. Appl Phys Lett 84(9):1609–1611. https://doi.org/10.1063/1.1650878
Geiger DK, Geiger HC, Williams L, Noll BC (2012) 2-(Thiophen-2-yl)-1- (thiophen-2-ylmethyl)-1H-benzimidazole. Acta Crystallogr Sect E: Struct Rep Online 68(2):o420–o420
Gill RE, Malliaras GG, Wildeman J, Hadziioannou G (1994) Tuning of photo-and electroluminescence in alkylated polythiophenes with well-defined regioregularity. Adv Mater 6(2):132–135
Güllüoglu MT, Özduran M, Kurt M, Kalaichelvan S, Sundaraganesan N (2010) Molecular structure and vibrational spectra of 2-and 5-methylbenzimidazole molecules by density functional theory. Spectrochim Acta Part A Mol Biomol Spectrosc 76(2):107–114. https://doi.org/10.1016/j.saa.2010.02.032
Heeger AJ (2001) Semiconducting and metallic polymers: the fourth generation of polymeric materials. J Phys Chem B 105(36):8475–8491. https://doi.org/10.1021/jp011611w
Hess BA Jr, Schaad LJ, Carsky P, Zahradnik R (1986) Ab initio calculations of vibrational spectra and their use in the identification of unusual molecules. Chem Rev 86(4):709–730
Hymete A, Rohloff J, Kjosen H et al (2005) Acetylenic thiophenes from the roots of Echinops ellenbeckii from Ethiopia. Nat Prod Res 19:755–761
James DK, Tour JM (2005) Molecular wires. Molecular wires and electronics. Springer Berlin Heidelberg, Berlin, Heidelberg, pp 33–62. https://doi.org/10.1007/b136066
Kaya S et al (2015) Determination of corrosion inhibition effects of amino acids: quantum chemical and molecular dynamic simulation study. J Taiwan Inst Chem Eng 58:528–535. https://doi.org/10.1016/j.jtice.2015.06.009
Koopmans T (1934) Über die Zuordnung von Wellenfunktionen und Eigenwerten zu den einzelnen Elektronen eines Atoms. Physica 1(1–6):104–113. https://doi.org/10.1016/S0031-8914(34)90011-2
Krishnakumar V, Prabavathi N (2010) Structure and vibrational frequencies of 6, 7- dimethoxy-1, 4-dihydro-1, 3-quinoxalinedione based on density functional theory calculations: The role of π-electron conjugation and back-donation. Spectrochim Acta Part A Mol Biomol Spectrosc 77(1):238–247. https://doi.org/10.1016/j.saa.2010.05.015
Kumar D, Jainb N, Jaina V, Raia B (2020) Amino acids as copper corrosion inhibitors: a density functional theory approach. App Sur Sci 514:145905. https://doi.org/10.1016/j.apsusc.2020.145905
Lee C, Yang W, Parr RG, Gazquez JL (1998) A hardness and softness theory of bond energies and chemical reactivity. Theol and Comp Chem 5:135–152. https://doi.org/10.1016/S1380-7323(98)80007-1
Li XH, Zhang XZ (2013) The spectroscopic, NMR analysis of 2-dicyanovinyl-5(4- methoxyphenyl) thiophene by density functional method. Spectrochim Acta A 105:280–287. https://doi.org/10.1016/j.saa.2012.12.048
Li XH, Liu XR, Zhang XZ (2011) Calculation of vibrational spectroscopic and NMR parameters of 2-dicyanovinyl-5-(4-N, N-dimethylaminophenyl) thiophene by ab initio HF and density functional methods. Comput Theor Chem 969(1–3):27–34. https://doi.org/10.1016/j.comptc.2011.05.010
Loto R (2019) Corrosion inhibition effect of non-toxic α-amino acid compound on high carbon steel in low molar concentration of hydrochloric acid. J Mater Res Technol 8:484–493. https://doi.org/10.1016/j.jmrt.2017.09.005
Masoud M, Awad M, Shaker M, El-Tahawy M (2010) The role of structural chemistry in the inhibitive performance of some aminopyrimidines on the corrosion of steel. Corrosion Sci 52:2387–2396. https://doi.org/10.1016/j.corsci.2010.04.011
McQuade DT, Pullen AE, Swager TM (2000) Conjugated polymer-based chemical sensors. Chem Rev 100(7):2537–2574. https://doi.org/10.1021/cr9801014. (PMID: 11749295)
Molvi KI, Vasu KK, Yerande SG, Sudarsanam V, Haque N (2007) Syntheses of new tetrasubstituted thiophenes as novel anti-inflammatory agents. Eur J Med Chem 42(8):1049–1058. https://doi.org/10.1016/j.ejmech.2007.01.007. (PMID: 17336429)
Mortimer FS, Blodgett RB, Daniels F (2002) The infrared spectra of fifteen organic bromides from 500 to 800 cm–1. J Am Chem Soc. 69:822–826. https://doi.org/10.1021/Ja01196A022
Nwankwo H, Olasunkanmi L, Ebenso E (2017) Experimental, quantum chemical and molecular dynamic simulations studies on the corrosion inhibition of mild steel by some carbazole derivatives. Sci Rep 7:2436. https://doi.org/10.1038/s41598-017-02446-0
Obot IB, Obi-Egbedi NO, Eseola AO (2011) Anticorrosion potential of 2-mesityl-1H- imidazo[4,5-f] [1,10] phenanthroline on mild steel in sulfuric acid solution: experimental and theoretical study. Ind Eng Chem Res 50:2098–2110. https://doi.org/10.1021/ie102034c
Ośmiałowski B, Kolehmainen E, Gawinecki R (2001) GIAO/DFT calculated chemical shifts of tautomeric species. 2‐Phenacylpyridines and (Z)‐2‐(2‐hydroxy‐2‐phenylvinyl)pyridines. Magnet Resonance Chem 39(6):334–340. https://doi.org/10.1002/mrc.856
Pearson RG (1997) Chemical hardness: applications from molecules to solids. Wiley- VCH, Weinheim
Pihlaja K, Kleinpeter E (eds) (1994) Carbon-13 NMR chemical shifts in structural and sterochemical analysis. VCH Publishers, Deerfield Beach
Pulay P, Zhou X, Fogarasin G in: Fransto R (eds) (1993) NATO AS Series, Kluwer, Dordrecht, C 406: 99
Radilla J, Negrón-Silva GE, Palomar-Pardavé M, Romero-Romo M, Galván M (2013) DFT study of the adsorption of the corrosion inhibitor 2-mercaptoimidazole onto Fe (100) surface. Electrochim Acta 112:577–586. https://doi.org/10.1016/j.electacta.2013.08.151
Rai NS, Kalluraya B, Lingappa B, Shenoy S, Puranic VG (2008) Convenient access to 1,3,4-trisubstituted pyrazoles carrying 5-nitrothiophene moiety via 1,3-dipolar cycloaddition of sydnones with acetylenic ketones and their antimicrobial evaluation. Euro J Medi Chem 43:1751–1720. https://doi.org/10.1002/chin.200852126
Reddinger JL, Reynolds JR, Wandrey C (1999) Radical polymerisation polyelectrolytes. In: Reddinger JL, Reynolds JR, Wandrey C (eds) Advances in Polymer Science. Springer, Berlin, Heidelberg
Robins RK (1986) Synthetic antiviral agents. Chem Eng News 64:28–40. https://doi.org/10.1021/cen-v064n004.p028
Sarojinidevi K, Subramani P, Jeeva M, Sundaraganesan N, SusaiBoobalan M, VenkatesaPrabhu G (2018) Synthesis, molecular structure, quantum chemical analysis, spectroscopic and molecular docking studies of N-(Morpholinomethyl) succinimide using DFT method. J Mol Struct 1175:609–623. https://doi.org/10.1016/j.molstruc.2018.07.101
Sathyanarayana DN (2004) Vibrational spectroscopy theory and applications. New Age International Publishers, New Delhi, pp 446–447
Shin DN, Hahn JW, Jung KH, Ha TK (1998) Study of the cis and trans conformers of 2-halophenols using coherent anti-Stokes Raman spectroscopic and quantum chemical methods. J Raman Spectrosc 29(4):245–249
Si P, Chi Q, Li Z, Ulstrup J, Moller PJ, Mortensen J (2007) Functional polythiophene nanoparticles: size-controlled electropolymerization and ion selective response. J Am Chem Soc 129:3888–3896
Silverstein RM, Bassler GC (1962) Spectrometric identification of organic compounds. J Chem Educ 39(11):546. https://doi.org/10.1021/ed039p546
Subramaninan N, Sundaraganesan N, Jayabharathi JA (2010) Molecular structure, spectroscopic (FT-IR, FT-Raman, NMR, UV) studies and first order molecular hyperpolarizabilities of 1,2-bis (3-methoxy-4-hydroxy benzlidene) hydrazine by density functional method. Spectrochim Acta A Mol Biomol Spectrosc 76:259–269. https://doi.org/10.1016/j.saa.2010.03.033
Sundaraganesan N, Kalaichelvan S, Meganathan C, Dominicm Joshua D, Cornard J (2008) FT-IR, FT-Raman spectra and ab initio HF and DFT calculations of 4-N N’-dimethylamino pyridine. Spectrochim Acta A 71:898. https://doi.org/10.1016/j.saa.2008.02.016
Unal A, Eren B (2013) FT-IR, dispersive Raman, NMR, DFT and antimicrobial activity studies on 2-(Thiophen-2-yl)-1H-benzo[d] imidazole. Spectrochim Acta A Mol Biomol Spectrosc 114:129–136. https://doi.org/10.1016/j.saa.2013.05.045
Varsányi G, Láng L, Kovner MAE, Lempert K (1974) Assignment for vibrational spectra of seven hundred benzene derivatives. Academic Kiaclo Vol. 1–2, Budapest
Venil K, Lakshmi A, Balachandran V, Narayana Vinutha B, Salian V (2021) FT-IR and FT-Raman investigation, quantum chemical analysis and molecular docking studies of 5-(4-Propan-2-yl) benzylidene)- 2-[3-(4-chlorophenyl)-5[4-(propan-2-yl) phenyl- 4,5-dihydro-1H-pyrazol-1-yl]-1,3-thiazol-4(5H)-one. J Mol Struct 1225:129070. https://doi.org/10.1016/j.molstruc.2020.129070
Wu Z, Fan B, Xue F, Adachi C, Ouyang J (2010) Organic molecules based on dithienyl-2, 1, 3-benzothiadiazole as new donor materials for solution-processed organic photovoltaic cells. Sol Energy Mater Sol Cells 94(12):2230–2237. https://doi.org/10.1016/j.solmat.2010.07.017
Xavier TS, Rashid N, Hubert Joe I (2011) Vibrational spectra and DFT study of anticancer active molecule 2-(4-Bromophenyl)-1H-benzimidazole by normal coordinate analysis. Spectrochim Acta A Molecul Biomolecul Spectrosc 78:319. https://doi.org/10.1016/j.saa.2010.10.013
Yang W, Mortier WJ (1986) The use of global and local molecular parameters for the analysis of the gas-phase basicity of amines. J Am Chem Soc 108(19):5708–5711. https://doi.org/10.1021/ja00279a008
Yang L, Feng JK, Ren AM (2005) Theoretical studies on the electronic and optical properties of two thiophene–fluorene based π-conjugated copolymers. Polymer 46(24):10970–10981. https://doi.org/10.1016/j.polymer.2005.09.050
Acknowledgements
We thank Cauvery College for Women (Autonomous), Tiruchirappalli, for providing instrument facility under the support of DST-FIST-Level 0 program (Ref. No. SR/FST/College-246/2015(c)).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
There is no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) 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.
About this article
Cite this article
Rakini Chanderasekaran, J.H., Devi, D. & Meenakshi, R. Molecular structure, spectroscopic investigation, frontier molecular orbital and global reactivity descriptors analysis of 2-(2-Nitrovinyl) thiophene for anti-corrosion and DSSC applications. Chem. Pap. 78, 3273–3296 (2024). https://doi.org/10.1007/s11696-024-03311-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11696-024-03311-x