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Investigation of second-order NLO properties of novel 1,3,4-oxadiazole derivatives: a DFT study

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Abstract

Context

In this study, we have developed four new chromophores (TM1–TM4) and performed quantum chemical calculations to explore their nonlinear optical properties. Our focus was on understanding the impact of electron-donating substituents on 1,3,4-oxadiazole derivative chromophores. The natural bond orbital analysis confirmed the interactions between donors and acceptors as well as provided insights into intramolecular charge transfer. We also estimated dipole moment, linear polarizability molecular electrostatic potential, UV–visible spectra, and first hyperpolarizability. Our results revealed that TM1 with a strong and stable electron-donating group exhibited high first hyperpolarizability (β) 293,679.0178 × 10−34 esu. Additionally, TM1 exhibited a dipolar moment (μ) of 5.66 Debye and polarizability (α) of 110.62 × 10−24 esu when measured in dimethyl sulfoxide (DMSO) solvent. Furthermore, in a benzene solvent, TM1 showed a low energy band gap of 5.33 eV by using the ωB97XD functional with a 6–311 +  + G(d, p) basis set. Moreover, our study of intramolecular charge transfers highlighted N, N dimethyl triphenylamine and carbazole as major electron-donating groups among the four 1,3,4-oxadiazole derivative chromophores. This research illustrates the potential applications of these organic molecules in photonics due to their versatile nature.

Methods

The molecules were individually optimized using different functionals, including APFD, B3LYP, CAM B3LYP, and ωB97XD combined with the 6–311 +  + G (d, p) basis set in Gaussian 16 software. These methods encompass long-range functionals such as APFD and B3LYP, along with long-range corrected functionals like CAM B3LYP and ωB97XD. The employed functionals of APFD, B3LYP, CAM B3LYP, and ωB97XD with the 6–311 +  + G (d,p) basis set were used to extract various properties such as geometrical structures, dipole moment, molecular electrostatic potential, and first hyperpolarizability through precise density functional theory (DFT). Additionally, TD-DFT was utilized for obtaining UV–visible spectra. All studies have been conducted in both gas and solvent phases.

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Data availability

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

References

  1. Wu J, Luo J, Jen AK-Y (2020) High-performance organic second-and third-order nonlinear optical materials for ultrafast information processing. J Mater Chem C 8(43):15009–15026

    Article  CAS  Google Scholar 

  2. Dini D, Barthel M, Schneider T, Ottmar M, Verma S, Hanack M (2003) Phthalocyanines and related compounds as switchable materials upon strong irradiation: the molecular engineering behind the optical limiting effect. Solid State Ionics 165(1–4):289–303

    Article  CAS  Google Scholar 

  3. Yahya M, Seferoğlu N, Barsella A, Achelle S, Seferoğlu Z (2021) Amino-substituted-1, 1-dicyano-2, 4-diaryl-1, 3-butadiene chromophores: Synthesis and photophysical properties. Spectrochim Acta Part A Mol Biomol Spectrosc 248:119178

    Article  CAS  Google Scholar 

  4. Basu S (1984) A review of nonlinear optical organic materials. Ind Eng Chem Prod Res Dev 23(2):183–186

    Article  CAS  Google Scholar 

  5. Liu F, Wang H, Yang Y, Xu H, Yang D, Bo S, Liu J, Zhen Z, Liu X, Qiu L (2015) Using phenoxazine and phenothiazine as electron donors for second-order nonlinear optical chromophore: enhanced electro-optic activity. Dyes Pigm 114:196–203

    Article  CAS  Google Scholar 

  6. Liu J, Ouyang C, Huo F, He W, Cao A (2020) Progress in the enhancement of electro-optic coefficients and orientation stability for organic second-order nonlinear optical materials. Dyes Pigm 181:108509

    Article  CAS  Google Scholar 

  7. Koos C, Vorreau P, Vallaitis T, Dumon P, Bogaerts W, Baets R, Esembeson B, Biaggio I, Michinobu T, Diederich F (2009) All-optical high-speed signal processing with silicon–organic hybrid slot waveguides. Nat Photon 3(4):216–219

    Article  CAS  Google Scholar 

  8. Najare MS, Patil MK, Tilakraj TS, Yaseen M, Nadaf AA, Mantur S, Inamdar SR, Khazi IAM (2021) Photophysical and electrochemical properties of highly π-conjugated bipolar carbazole-1, 3, 4-oxadiazole-based d-π-a type of efficient deep blue fluorescent dye. J Fluoresc 31:1645–1664

  9. Jia YJ, Chen YG, Guo Y, Guan XF, Li C, Li B, Liu MM, Zhang XM (2019) LiMII (IO3) 3 (MII= Zn and Cd): two promising nonlinear optical crystals derived from a tunable structure model of α-LiIO3. Angew Chem Int Ed 58(48):17194–17198

    Article  CAS  Google Scholar 

  10. Marder SR, Perry JW, Tiemann BG, Marsh RE, Schaefer WP (1990) Second-order optical nonlinearities and photostabilities of 2-N-methylstilbazolium salts. Chem Mater 2(6):685–690

    Article  CAS  Google Scholar 

  11. Waddar B, Parne SR, Gandi S, Prasanth GR, Yaseen M, Kariduraganavar MY (2023) The second-order nonlinear optical properties of novel triazolo [3, 4-b][1, 3, 4] thiadiazole derivative chromophores using DFT calculations. Struct Chem 35:253–264

  12. Bella SD (2001) Second-order nonlinear optical properties of transition metal complexes. Chem Soc Rev 30(6):355–366

    Article  Google Scholar 

  13. Bureš F, Čermáková H, Kulhánek J, Ludwig M, Kuznik W, Kityk IV, Mikysek T, Růžička A (2012) Structure–property relationships and nonlinear optical effects in donor‐substituted dicyanopyrazine‐derived push–pull chromophores with enlarged and varied π‐linkers. Eur J Org Chem 2012(3):529–538

  14. Kim TD, Lee KS (2015) D-π-A conjugated molecules for optoelectronic applications. Macromol Rapid Commun 36(11):943–958

    Article  CAS  PubMed  Google Scholar 

  15. Mishra A, Ma C-Q, Bauerle P (2009) Functional oligothiophenes: molecular design for multidimensional nanoarchitectures and their applications. Chem Rev 109(3):1141–1276

    Article  CAS  PubMed  Google Scholar 

  16. Pron A, Gawrys P, Zagorska M, Djurado D, Demadrille R (2010) Electroactive materials for organic electronics: preparation strategies, structural aspects and characterization techniques. Chem Soc Rev 39(7):2577–2632

    Article  CAS  PubMed  Google Scholar 

  17. Mikroyannidis JA, Spiliopoulos IK, Kasimis TS, Kulkarni AP, Jenekhe SA (2003) Synthesis, photophysics, and electroluminescence of conjugated poly (p-phenylenevinylene) derivatives with 1, 3, 4-oxadiazoles in the backbone. Macromolecules 36(25):9295–9302

    Article  CAS  Google Scholar 

  18. Najare MS, Patil MK, Garbhagudi M, Yaseen M, Inamdar SR, Khazi IAM (2021) Design, synthesis and characterization of π-conjugated 2, 5-diphenylsubstituted-1, 3, 4-oxadiazole-based D-π-A-π’-D′ form of efficient deep blue functional materials: photophysical properties and fluorescence “Turn-off” chemsensors approach. J Mol Liq 328:115443

    Article  CAS  Google Scholar 

  19. Najare MS, Patil MK, Nadaf AA, Mantur S, Garbhagudi M, Gaonkar S, Inamdar SR, Khazi IAM (2020) Photophysical, thermal properties, solvatochromism and DFT/TDDFT studies on novel conjugated DA-π-AD form of small molecules comprising thiophene substituted 1, 3, 4-oxadiazole. J Mol Struct 1199:127032

    Article  CAS  Google Scholar 

  20. Oliveira MS, Santos AB, Ferraz TV, Moura GL, Falcão EH (2023) Non-symmetrical 1, 3, 4-oxadiazole derivatives: synthesis, characterization, and computational study of their optical properties. Chem Phys Impact 6:100162

    Article  Google Scholar 

  21. Khemalapure SS, Hiremath SM, Hiremath CS, Katti VS, Basanagouda MM (2020) Investigations of structural, vibrational and electronic properties on 5-(6-methyl-benzofuran-3-ylmethyl)-3H-[1, 3, 4] oxadiazole-2-thione: experimental and computational approach. Chem Data Collect 28:100410

    Article  CAS  Google Scholar 

  22. Alongamo CHA, Nkungli NK, Ghogomu JN (2019) DFT-based study of the impact of transition metal coordination on the charge transport and nonlinear optical (NLO) properties of 2-{[5-(4-nitrophenyl)-1, 3, 4-thiadiazol-2-ylimino] methyl} phenol. Mol Phys 117(18):2577–2592

    Article  CAS  Google Scholar 

  23. Carella A, Castaldo A, Centore R, Fort A, Sirigu A, Tuzi A (2002) Synthesis and second order nonlinear optical properties of new chromophores containing 1, 3, 4-oxadiazole and thiophene rings. J Chem Soc Perkin Trans 2(11):1791–1795

    Article  Google Scholar 

  24. Fang Y-K, Liu C-L, Chen W-C (2011) New random copolymers with pendant carbazole donor and 1, 3, 4-oxadiazole acceptor for high performance memory device applications. J Mater Chem 21(13):4778–4786

    Article  CAS  Google Scholar 

  25. Homocianu M, Airinei A, Ipate AM, Hamciuc C (2022) Spectroscopic recognition of metal ions and non-linear optical (NLO) properties of some fluorinated poly (1, 3, 4-oxadiazole-ether) s. Chemosensors 10(5):183

    Article  CAS  Google Scholar 

  26. Dhannur SH, Shridhar A, Suresh S, Al-Asbahi BA, Al-Hada NM, Shelar VM, Naik L (2024) DFT studies on D–π–A substituted bis-1, 3, 4-oxadiazole for nonlinear optical application. J Opt 1–11. https://doi.org/10.1007/s12596-024-01698-0

  27. Homocianu M, Airinei A, Hamciuc C, Ipate AM (2019) Nonlinear optical properties (NLO) and metal ions sensing responses of a polymer containing 1, 3, 4-oxadiazole and bisphenol A units. J Mol Liq 281:141–149

    Article  CAS  Google Scholar 

  28. Barbosa-Silva R, Oliveira MS, Ferreira RC, Manzoni V, Falcão EH, de Araújo CB (2023) Second-order optical nonlinearity of two 1, 3, 4-oxadiazole derivatives: an experimental and theoretical study. Opt Mater 146:114536

    Article  CAS  Google Scholar 

  29. Kohn W, Becke AD, Parr RG (1996) Density functional theory of electronic structure. J Phys Chem 100(31):12974–12980

    Article  CAS  Google Scholar 

  30. Kotteswaran S, Ramasamy P (2021) The influence of triphenylamine as a donor group on Zn–porphyrin for dye sensitized solar cell applications. New J Chem 45(5):2453–2462

    Article  CAS  Google Scholar 

  31. Yang Y, Xu W, Zhao J, Liu J (2019) Using phenothiazine as electron donor for new second-order nonlinear optical chromophore. Mater Lett 245:196–199

    Article  CAS  Google Scholar 

  32. Kukhta A, Kukhta I, Kukhta N, Neyra O, Meza E (2008) DFT study of the electronic structure of anthracene derivatives in their neutral, anion and cation forms. J Phys B: At Mol Opt Phys 41(20):205701

    Article  Google Scholar 

  33. Huang Z, Gu Y, Liu X, Zhang L, Cheng Z, Zhu X (2017) Metal-free atom transfer radical polymerization of methyl methacrylate with ppm Level of organic photocatalyst. Macromol Rapid Commun 38(10):1600461

    Article  Google Scholar 

  34. Garza AJ, Osman OI, Wazzan NA, Khan SB, Asiri AM, Scuseria GE (2014) A computational study of the nonlinear optical properties of carbazole derivatives: theory refines experiment. Theoret Chem Acc 133:1–8

    Article  CAS  Google Scholar 

  35. Mahmood A, Khan SUD, Rana UA, Janjua MRSA, Tahir MH, Nazar MF, Song Y (2015) Effect of thiophene rings on UV/visible spectra and non-linear optical (NLO) properties of triphenylamine based dyes: a quantum chemical perspective. J Phys Org Chem 28(6):418–422

    Article  CAS  Google Scholar 

  36. Ledwon P (2019) Recent advances of donor-acceptor type carbazole-based molecules for light emitting applications. Org Electron 75:105422

    Article  CAS  Google Scholar 

  37. Blanchard P, Malacrida C, Cabanetos C, Roncali J, Ludwigs S (2019) Triphenylamine and some of its derivatives as versatile building blocks for organic electronic applications. Polym Int 68(4):589–606

    Article  CAS  Google Scholar 

  38. Me F, Trucks G, Schlegel HB, Scuseria G, Robb M, Cheeseman J, Scalmani G, Barone V, Petersson G, Nakatsuji H (2016) Gaussian 16. Gaussian, Inc., Wallingford, CT

    Google Scholar 

  39. Marenich AV, Cramer CJ, Truhlar DG (2009) Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J Phys Chem B 113(18):6378–6396

    Article  CAS  PubMed  Google Scholar 

  40. Jiang X, Zhao S, Lin Z, Luo J, Bristowe PD, Guan X, Chen C (2014) The role of dipole moment in determining the nonlinear optical behavior of materials: ab initio studies on quaternary molybdenum tellurite crystals. J Mater Chem C 2(3):530–537

    Article  CAS  Google Scholar 

  41. Acemioğlu B, Arık M, Efeoğlu H, Onganer Y (2001) Solvent effect on the ground and excited state dipole moments of fluorescein. J Mol Struct (Thoechem) 548(1–3):165–171

    Article  Google Scholar 

  42. Ahn M, Kim M-J, Cho DW, Wee K-R (2020) Electron push–pull effects on intramolecular charge transfer in perylene-based donor–acceptor compounds. J Org Chem 86(1):403–413

    Article  PubMed  Google Scholar 

  43. Parthasarathy V, Pandey R, Das PK, Castet F, Blanchard-Desce M (2018) Linear and nonlinear optical properties of tricyanopropylidene-based merocyanine dyes: synergistic experimental and theoretical investigations. ChemPhysChem 19(2):187–197

    Article  CAS  PubMed  Google Scholar 

  44. Drissi M, Benhalima N, Megrouss Y, Rachida R, Chouaih A, Hamzaoui F (2015) Theoretical and experimental electrostatic potential around the m-nitrophenol molecule. Molecules 20(3):4042–4054

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  45. Shimizu A, Ishizaki Y, Horiuchi S, Hirose T, Matsuda K, Sato H, Yoshida J-i (2020) HOMO–LUMO energy-gap tuning of π-conjugated zwitterions composed of electron-donating anion and electron-accepting cation. J Org Chem 86(1):770–781

    Article  PubMed  Google Scholar 

  46. Kaya S, Kaya C (2015) A new method for calculation of molecular hardness: a theoretical study. Comput Theor Chem 1060:66–70

    Article  CAS  Google Scholar 

  47. Pearson RG (1990) Hard and soft acids and bases—the evolution of a chemical concept. Coord Chem Rev 100:403–425

    Article  CAS  Google Scholar 

  48. Pegu D, Deb J, Van Alsenoy C, Sarkar U (2017) Theoretical investigation of electronic, vibrational, and nonlinear optical properties of 4-fluoro-4-hydroxybenzophenone. Spectrosc Lett 50(4):232–243

    Article  CAS  Google Scholar 

  49. Gázquez JL (1993). Hardness and softness in density functional theory. In: Sen KD (ed) Chemical Hardness. Structure and Bonding, vol 80. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0036798

  50. Domingo LR, Chamorro E, Pérez P (2008) Understanding the reactivity of captodative ethylenes in polar cycloaddition reactions A theoretical study. J Org Chem 73(12):4615–4624

    Article  CAS  PubMed  Google Scholar 

  51. Demircioğlu Z, Kaştaş ÇA, Büyükgüngör O (2015) Theoretical analysis (NBO, NPA, Mulliken Population Method) and molecular orbital studies (hardness, chemical potential, electrophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2-methylphenylimino) methyl)-3-methoxyphenol. J Mol Struct 1091:183–195

    Article  Google Scholar 

  52. Sheela N, Muthu S, Sampathkrishnan S (2014) Molecular orbital studies (hardness, chemical potential and electrophilicity), vibrational investigation and theoretical NBO analysis of 4–4′-(1H–1, 2, 4-triazol-1-yl methylene) dibenzonitrile based on abinitio and DFT methods. Spectrochim Acta Part A Mol Biomol Spectrosc 120:237–251

    Article  CAS  Google Scholar 

  53. Rizwana BF, Prasana JC, Muthu S, Abraham CS (2019) Spectroscopic (FT-IR, FT-Raman, NMR) investigation on 2-[(2-amino-6-oxo-6, 9-dihydro-3H-purin-9-yl) methoxy] ethyl (2S)-2-amino-3-methylbutanoate by density functional theory. Mater Today: Proc 18:1770–1782

    Google Scholar 

  54. Chocholoušová J, Špirko V, Hobza P (2004) First local minimum of the formic acid dimer exhibits simultaneously red-shifted O-H⋯ O and improper blue-shifted C–H⋯ O hydrogen bonds. Phys Chem Chem Phys 6(1):37–41

    Article  Google Scholar 

  55. Gelfand N, Freidzon A, Vovna V (2019) Theoretical insights into UV–Vis absorption spectra of difluoroboron β-diketonates with an extended π system: an analysis based on DFT and TD-DFT calculations. Spectrochim Acta Part A Mol Biomol Spectrosc 216:161–172

    Article  CAS  Google Scholar 

  56. Kariduraganavar MY, Doddamani RV, Waddar B, Parne SR (2021) Nonlinear optical responsive molecular switches. IntechOpen. https://doi.org/10.5772/intechopen.92675

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Acknowledgements

The authors express their thankfulness for the provision of computational facilities and Gaussian 16 under DST-FIST at the School of Chemical Sciences (formerly Department of Chemistry), Goa University. The authors gratefully thank Prof. Mahadevappa Y. Kariduraganavar and the Chairman, Department of PG Studies in Chemistry and Coordinator of Molecular Modelling Lab under the UPE FAR-I & DST PURSE Phase-II Programme at Karnatak University Dharwad, for providing the computational facility to the present work.

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Authors and Affiliations

  1. Department of Applied Sciences, National Institute of Technology Goa, Kottamoll Plateau, Cuncolim, Goa, 403703, India

    Balachandar Waddar, Suman Gandi & Saidi Reddy Parne

  2. School of Chemical Sciences, Goa University, Taleigao Plateau, Goa, 403206, India

    Vishnu Rama Chari

  3. Department of Electronics & Communication Engineering, National Institute of Technology Goa, Kottamoll Plateau, Cuncolim, Goa, 403703, India

    Gurusiddappa R. Prasanth

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  1. Balachandar Waddar
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Contributions

Balachandar Waddar and Saidi Reddy Parne conceived and designed this project. Balachandar Waddar carried out the molecular simulations and drafted the manuscript. Suman Gandi and Vishnu Rama Chari discussed the simulation results and gave valuable suggestions. Saidi Reddy Parne and Guru Siddappa R. Prasanth supervised the molecular simulations and revised the manuscript. All authors approved the final version of the manuscript.

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Correspondence to Saidi Reddy Parne.

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Waddar, B., Gandi, S., Parne, S.R. et al. Investigation of second-order NLO properties of novel 1,3,4-oxadiazole derivatives: a DFT study. J Mol Model 30, 118 (2024). https://doi.org/10.1007/s00894-024-05910-7

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