Vol. 25 No. 2 (2026): Mapana Journal of Sciences
Research Articles

Dipole Moments and Computational Study of 4(3IP)6MC and 4(3IP)6CLC Iodinated Coumarin Derivatives

  • Manjula Katageri,
  • Srinath,
  • Shivaleela B,
  • Sulochana Devar,
  • S. M. Hanagodimath
Manjula Katageri
Govt.First Grade Residential SC/ST's Model College college,HADALAGERI,Dist:Vijayapura
Srinath
Department of P G Studies and Research in Physics, Gulbarga University, Kalaburagi 585106, Karnataka, India
Shivaleela B
Department of P G Studies and Research in Physics, Gulbarga University, Kalaburagi 585106, Karnataka, India
Sulochana Devar
Department of P G Studies and Research in Physics, Gulbarga University, Kalaburagi 585106, Karnataka, India
S. M. Hanagodimath
Department of P G Studies and Research in Physics, Gulbarga University, Kalaburagi 585106, Karnataka, India

Published 2026-05-29

Keywords

  • Iodinated coumarin derivative,
  • Solvatochromism,
  • Dipole moment,
  • Density functional theory (DFT),
  • Non linear optical (NLO) properties

Copyright (c) 2026

Creative Commons License

This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.

Abstract

The comparative spectroscopic properties of the iodinated coumarin derivatives, viz., 4-(3-Iodo-phenoxymethyl)-6-methyl-chromen-2-one [4(3IP)6MC] and 6-Chloro-4-(3-iodo-phenoxymethyl)-chromen-2-one [4(3IP)6ClC], were investigated. Ground-state and excited-state dipole moments were evaluated by employing the solvatochromic shift method through the Lippert, Bakshiev, and Kawski–Chamma–Viallet equations in pure organic solvents at room temperature. Both compounds exhibited a bathochromic shift as a result of the excited-state dipole moments being greater than the ground-state dipole moments. This suggests a higher polarity in the excited state and validates the existence of intramolecular charge transfer. The change of dipole moment was 4.4D for 4(3IP)6MC and 4.9D for 4(3IP)6CLC. The Kamlet-Taft and Catalán linear solvation energy relationship model was further analyzed, revealing that hydrogen bonding interactions dominate over the dielectric interactions and dipolarity contributes to a lesser extent than polarizability for both molecules. The theoretical computational study was carried out with Gaussian 16W at the DFT/B3LYP/3-21G level. The frontier molecular orbitals (FMO) and nonlinear optical (NLO) parameters were evaluated. The results show notable enhanced parameters for 4(3IP)6CLC, indicating its potential as an efficient NLO material for advanced optical and imaging applications.

References

  1. Mohd Aqib, Khatoon S, et al. (2025),Exploring the anticancer potential and mechanisms of action of natural coumarins and isocoumarins, Europiean Journal of medicinal Chemistry Vol. 282.,117088,https://doi.org/10.1016/j.ejmech.2024.117088
  2. Ljungman M (2009) Targeting the DNA danger response in cancer, Chem. Rev.109, 2929-2950, https://doi.org/10.1021/cr900047g
  3. Woo Y, Chaurasiya S, O’Leary M, Han E, Fong Y (2021), Fluorescent Imaging for Cancer Therapy and Cancer Gene Therapy, https://doi.org/10.1016/j.omto.2021.06.007
  4. Makandar S N, Basanagouda M, Kulkarni M V, Pranesha, Rasal V P (2012) Synthesis and antimicrobial studies of some 4-aryloxymethyl coumarins obtained by reaction of 4-bromomethyl coumarins with aromatic bidental enucleophiles, Med.chem.Res 21, 2603-2614, https://doi.org/10.1007/s00044-011-9785
  5. Basanagouda M, Kulkarni M V, Sharma D, Gupta V K, Pranesha, Sandhya Rani P S, Rasal V P (2009) Synthesis of some new 4-aryloxymethyl coumarins and examination of their antibacterial and antifungal activitiez, J. Chem. Sci., Vol 121,pp 485-495. https://doi.org/10.1007/s12039-009-0058
  6. Basanagouda M, Jambagi V B, Barigidad N N, Laxmeshwar S S, Devaru V, Narayanachar (2014) Synthesis, structure-activity relationship of iodinated-4aryloxymethyl-coumarins as potential anti-cancer and anti-mycobacterial agents, Eur. J. Med. Chem., Vol 74, pp 225-233. https://doi.org/10.1016/j.ejmech.2013.12.06
  7. Lakowicz J R (1983)Principle of Fluorescence Spectroscopy, Plenum Press, New York,.
  8. Lippert E, Naturforsch Z,(1955) Dipole moment und Elektronenstruktur von angeregten Molekülen,10, 541–545.DOI: 10.1515/zna-1955-0707 (1955) 1-5
  9. Bakshiev N G (1964) Universal intermolecular interactions and their effect on the position of the electronic spectra of molecules in two-component solutions, Optics and Spectroscopy 16, 821–832,
  10. Chamma A, Viallet P (1970) Determination of the dipole moment of a molecule in a singlet excited state. C R Acad Sci Paris Ser C 270:1901–1904
  11. Bilot A K, Kawski A (1962). Z Naturforsch A 17A:621–627. https://doi.org/10.1515/zna-1962-0713
  12. Reichardt C (1988) Solvents and Solvent Effects in Organic Chemistry. Verlag Chemie, Weinheim, New York
  13. Taft R W, Abboud JL M, Kamlet M J, Abraham M H (1985) Linear solvation energy relationships. J Solution Chem. 14:153–186. https://doi.org/10.1007/BF00647061
  14. Catalán J (2009) Toward a generalized treatment of the solvent effect based on four empirical scales: dipolarity (SdP, a new scale), polarizability (SP), acidity (SA), and basicity (SB) of the medium. The Journal of Physical Chemistry B 113(17):5951–5960. https://doi.org/10.1021/jp8095727
  15. Robb M A (1916) New chemistry with Gaussian 16 and Gauss View 6. Accessed 25 Sept 2022.
  16. Zaier R, Ayachi S (2021) Computational study on optoelectronic properties of donor–acceptor type small π-conjugated molecules for organic light-emitting diodes (OLEDs) and nonlinear optical (NLO) applications. In: Density Functional Theory - Recent Advances, New Perspectives and Applications.
  17. Mahantesha Basanagouda, Vishwanath B. Jambagi, Nivedita N. et.al (2014) Synthesis, structure activity relationship of iodinated-4- aryloxymethyl-coumarins as potential anti-cancer and antimycobacterial agents, European Journal of Medicinal Chemistry 74 (2014) 225 e233 , http://www.elsevier.com/locate/ejmech
  18. Nagachandra K H, Mannekutla J R, Amarayya S M, Inamdar S R (2012) Solvent effect on the spectral properties of dipolar laser dyes: Evaluation of ground and excited state dipole moments. European Journal of Chemistry 3(2):163–171.
  19. https://doi.org/10.5155/eurjchem.3.2.163.538
  20. Wari M N, Inamdar S R (2017) Solvatochromic study of organic dyes: A qualitative approach using semi empirical (ZINDO-IEFPCM) method. International Journal of Pure and Applied Research in Physics 4(1):51–56. ISSN 2455-474X.
  21. Thipperudrappa J, Deepa H R, Raghavendra U P, Hanagodimath S M, Melavanki R M (2016) Effect of solvents, solvent mixture and silver nanoparticles on photophysical properties of a ketocyanine dye. Luminescence. https://doi.org/10.1002/bio.3147
  22. Mathapati G B, Ingalagondi P K, et al (2019) Estimation of ground and excited state dipole moments of newly synthesized coumarin molecule by solvatochromic method and Gaussian software. International Journal of Scientific Research in Physics and Applied Sciences 7(2):3843. https://doi.org/10.26438/ijsrpas/v7i2.3843
  23. Devar S, More S, Patil O, Nagesh G Y, Hanagodimath S M (2025) Synthesis, spectroscopic, DFT calculation and molecular docking studies of indole derivative. Journal of Fluorescence. https://doi.org/10.1007/s10895-025-04301-2
  24. More S, Patil O, Devar S, Hanagodimath S M (2024) Estimation of electric dipole moment by solvatochromism, computational method, and study of the effect of solvents by preferential solvation of 6-methoxy-4-(4-nitrophenoxy methyl)-chromen-2-one (6MNPM). Journal of Fluorescence. https://doi.org/10.1007/s10895-024-03955-8
  25. Edward J T (1956) Molecular volumes and parachor. Chemistry and Industry (London) 774.
  26. Ravi M, Samanta A, Radhakrishnan TP (1995). Journal of the Chemical Society, Faraday Transactions 91:2739. https://doi.org/10.1039/FT9959102739
  27. Reichardt C (1994) Solvatochromic dyes as solvent polarity indicators. Chemical Reviews 94(8):2319–2358. https://doi.org/10.1021/cr00032a005.
  28. Waghorne, W.E., 2024. Solvent acidity and basicity scales: Analysis of Catalan’s SB and SA scales and comparison with Kamlet–Taft β and α scales. J. Solution Chem. 53, 747–760. https://doi.org/10.1007/s10953-024-01382-8.
  29. Homocianu, M., et al., 2023. Solvatochromism correlated with Kamlet–Taft and Catalán solvent scales. Int. J. Mol. Sci. 24, 5286. https://doi.org/10.3390/ijms24065286.
  30. Parr R G, Szentpály L V, Liu S (1999) Electrophilicity index. Journal of the American Chemical Society 121(9):1924–1932. https://doi.org/10.1021/ja983494x.
  31. More S, Patil O, Chillargikar S, Lalasangi D, Hanagodimath S M (2025) DFT-based quantum chemical analysis of coumarin derivatives. The Nucleus 62(1):37–46. https://doi.org/10.71330/thenucleus.2025.1445.
  32. Devar S, More S, Patil O, Nagesh G Y, Hanagodimath S M (2023) Quantum chemical calculation and molecular docking studies of indole derivative. European Chemical Bulletin 12(Special Issue 5):6704–6717. https://doi.org/10.48047/ecb/2023.12.si5a.0603.
  33. Basavaraj S, Gonnalli S, Patil O, Hanagodimath S M (2021) Quenching of fluorescence, dipole moments and DFT studies of newly synthesized amino-thiadiazole coumarin derivative. Journal of the Maharaja Sayajirao University of Baroda 55(1). ISSN 0025-0422
  34. Ayachit N H (2010) Excited state electric dipole moments of two laser dyes from solvatochromic shifts. Journal of Electron Spectroscopy and Related Phenomena 180:14–16. https://doi.org/10.1016/j.elspec.2010.01.004
  35. Shashirekha V, Umadevi M, Ramakrishnan V (2008) Solvatochromic study of 1,2-dihydroxyanthraquinone in neat and binary solvent mixtures. Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy 69:148
  36. https://doi.org/10.1016/j.saa.2007.03.021
  37. Tsague L F, Ejuh G W, Teyou Ngoupo A, Tadjouteu Assatse Y, Yossa Kamsi R A, Ottou Abe M T, Ndjaka J M B (2023) Ab-initio and density functional theory (DFT) computational study of the effect of fluorine on the electronic, optical, thermodynamic, hole and electron transport properties of the circumanthracene molecule. Heliyon 9:e19647. https://doi.org/10.1016/j.heliyon.2023.e19647
  38. Patil O, Ingalagondi P K, Mathapati G B, Hanagodimath S M (2018) Estimation of ground and excited state dipole moments of newly synthesized coumarin (4-MPMHC) derivative. JETIR 5(9).
  39. Shivaleela B, Hanagodimath S M (2020) Ground state and excited state dipole moments of coumarin derivative 4ATMC. In: Proceedings of the International Conference on Advanced Materials, pp 240–248.
  40. J.Tipperudrappa, U.P.Raghavendra, Mahantesh Basanagouda (2014) Photophysical characteristics of biologically active 4-aryloxymethyl coumarin 4PTMBC and 1IPMBC, Spectrochim Acta A Mol Biomol Spectrosc . DOI: 10.1016/j.saa.2014.10.039
  41. Chandrasekhar, S.; Deepa, H. R.; Melavanki, R. M.; Mogurampelly, S.; Basanagouda, M. M.; Yallappa, S.; Thipperudrappa, J. “Quantum chemical and solvatochromic studies of biologically active 1,3,4-thiadiazol coumarin derivatives”. Chemical Data Collections 2020, 29, 100516. https://doi.org/10.1016/j.cdc.2020.100516
  42. Shivaleela B, Shivaraj G G, Hanagodimath S M (2023) Estimation of dipole moments by solvatochromic shift method, spectroscopic analysis of UV–visible, HOMO–LUMO, ESP map, Mulliken atomic charges, NBO, NLO properties of benzofuran derivative. Results in Chemistry 6:101046. https://doi.org/10.1016/j.rechem.2023.101046
  43. Gonnalli S G, Basavaraj S, Hanagodimath S M Spectroscopic analysis of NMR, IR, UV–Vis, HOMO–LUMO, ESP and Mulliken charges of coumarin derivatives by density functional theory. Journal of the Maharaja Sayajirao University of Baroda. ISSN 0025-0422.
  44. Choudhary V K, Bhatt A K, Dash D, Sharma N (2019) DFT calculations on molecular structure, HOMO–LUMO study, reactivity descriptions and spectral analysis of newly synthesized diorganotin(I V) 2-chloridophenylacetohydroxamate complexes. Journal of Computational Chemistry 40(27):2354–2363. https://doi.org/10.1002/jcc.26012
  45. Jayarajan R, Satheeshkumar R, Kottha T, Subbaramanian S, Sayin K, Vasuki G (2020) Water mediated synthesis of 6-amino-5-cyano-2-oxo-N-(pyridin-2-yl)-4-(p-tolyl)-2H-[1,2′-bipyridine]-3-carboxamide and 6-amino-5-cyano-4-(4-fluorophenyl)-2-oxo-N-(pyridin-2-yl)-2H-[1,2′-bipyridine]-3-carboxamide – An experimental and computational studies with nonlinear optical (NLO) and molecular docking analyses. Spectrochimica Acta Part A: Molecular and Bimolecular Spectroscopy 229:117861.
  46. https://doi.org/10.1016/j.saa.2019.117861.
  47. Balachandar Waddar, Suman Gandi, S. R. Parne, V. R. Chari, G. R. Prasanth (2024) Investigation of Second-Order NLO Properties of Novel 1,3,4-Oxadiazole Derivatives: A DFT Study (2024) Journal of Molecular Modeling, Vol 30, Article 118
  48. DOI: 10.1007/s00894-024-05910-7

Most read articles by the same author(s)