Skip to main content
SpringerLink
Log in

Thermal, physicochemical and spectroscopic studies on some novel organic complexes obtained by green synthesis

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

The solid–liquid equilibrium phase diagram and thermochemical studies on two binary organic systems involving N-methylurea (MU) with 4-nitrophenol (NP) and 3-nitrobenzoic acid NBA were studied. Both systems show the formation of an equimolar intermolecular compound (IMC) and two eutectics (E1 and E2) one on either side of the IMC. Thermodynamic parameters such as heat of mixing, entropy of fusion, roughness parameter, interfacial energy and excess thermodynamic functions of intermolecular compounds and eutectics were calculated using the experimentally determined enthalpy of fusion by the DSC method. The spectroscopic studies, FTIR and NMR, of both the IMCs along with their parent compounds revealed the hydrogen bonding association between the parent moieties forming the complex. The findings were also confirmed by the appearance of new peaks in the powder XRD of the complexes in addition to their parent compounds.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Cave GWV, Raston CL, Scott JL. Recent advances in solventless organic reactions: towards benign synthesis with remarkable versatility. Chem Commun. 2001;21:2159–69.

    Article  CAS  Google Scholar 

  2. Anastas PT, Warner JC. Green chemistry: theory and practice. New York: Oxford University Press; 1998.

  3. Clark JH. Green chemistry: challenges and opportunities. Green Chem. 1999;1(1):1–8.

    Article  CAS  Google Scholar 

  4. Garay AL, Pichon A, James SL. Solvent-free synthesis of metal complexes. Chem Soc Rev. 2007;36(6):846–55.

    Article  PubMed  Google Scholar 

  5. Houton KA, Burslem GM, Wilson AJ. Development of solvent-free synthesis of hydrogen-bonded supramolecular polyurethanes. Chem Sci. 2015;6(4):2382–8.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  6. Tanaka K, Toda F. Solvent-free organic synthesis. Chem Rev. 2000;100(3):1025–74.

    Article  CAS  PubMed  Google Scholar 

  7. Desiraju GR. A bond by any other name. Angew Chem Int Ed. 2011;50(1):52–9.

    Article  CAS  Google Scholar 

  8. Rai US, Singh M, Rai RN. Remarkable dielectric properties of 1: 2 inter-molecular compound of 2-(4-(dimethylamino)benzylideneamino) benzoic acid and urea due to excited-state intramolecular proton transfer. RSC Adv. 2017;7(55):34382–91.

    Article  CAS  Google Scholar 

  9. Rai RN, Ramasamy P, Lan CW. Synthesis and crystal growth of binary organic NLO material UNBA. J Cryst Growth. 2002;235(1):499–504.

    Article  CAS  Google Scholar 

  10. Singh NB, Glicksman ME, Mazelsky R. Solidification behaviour of organic nonlinear optical crystals. Prog Cryst Growth Charact Mater. 1988;17(4):265–78.

    Article  CAS  Google Scholar 

  11. Nandi N, Bhattacharyya K, Bagchi B. Dielectric relaxation and solvation dynamics of water in complex chemical and biological systems. Chem Rev. 2000;100(6):2013–46.

    Article  CAS  PubMed  Google Scholar 

  12. Chemla DS, Zyss J. Nonlinear optical properties of organic molecules and crystals academic. New York: Elsevier; 1987.

    Google Scholar 

  13. Maeda M. Laser dyes. New York: Academic Press; 1984.

    Google Scholar 

  14. Winnik FM, Regismond ST. Fluorescence methods in the study of the interactions of surfactants with polymers. Colloids Surf A. 1996;118(1):1–39.

    Article  CAS  Google Scholar 

  15. Saroja G, et al. The fluorescence response of a structurally modified 4-aminophthalimide derivative covalently attached to a fatty acid in homogeneous and micellar environments. J Phys Chem B. 1999;103(15):2906–11.

    Article  CAS  Google Scholar 

  16. Singh NB, et al. Nonlinear optical characteristics of binary organic systems. J Cryst Growth. 1993;128:976–80.

    Article  CAS  Google Scholar 

  17. Dwivedi Y, et al. Synthesis, physicochemical and optical characterization of novel fluorescing complex: o-phenylenediamine–benzoin. J Fluoresc. 2011;21(3):1255–63.

    Article  CAS  PubMed  Google Scholar 

  18. Henningsen T, et al. Growth of binary organic NLO crystals: mNa-pNA and mNa-CNA systems. Mater Lett. 1994;20(3-4):203–9.

    Article  CAS  Google Scholar 

  19. Huiszoon C, Tiemessen GWM. Monomethylurea: a redetermination. Acta Crystallogr Sect B Struct Crystallogr Cryst Chem. 1976;32(5):1604–6.

    Article  Google Scholar 

  20. Wojcik G, Mossakowska I. Polymorphs of p-nitrophenol as studied by variable-temperature X-ray diffraction and calorimetry: comparison with m-nitrophenol. Acta Crystallogr B. 2006;62(1):143–52.

    Article  CAS  PubMed  Google Scholar 

  21. Dhaneshwar NN, et al. The crystal structure of a second modification of m-nitrobenzoic acid. Acta Crystallogr Sect B: Struct Crystallogr Cryst Chem. 1975;31(7):1978–80.

    Article  Google Scholar 

  22. Dean JA. Lange’s handbook of chemistry. New York: McGraw-Hill; 1985.

    Google Scholar 

  23. Rai US, Singh M, Rai RN. Some physicochemical studies on organic eutectics and inter-molecular compounds. J Therm Anal Calorim. 2017;130(2):967–72.

    Article  CAS  Google Scholar 

  24. Rai US, Rai RN. Physical chemistry of organic eutectic and monotectic: hexamethylbenzene–succinonitrile system. Chem Mater. 1999;11(11):3031–6.

    Article  CAS  Google Scholar 

  25. Neupane U, Rai RN. Synthesis, spectral characterization, thermal and optical studies of novel complexes: 4-(dimethylamino)benzylidene- 4-acetamideaniline and 4-(dimethylamino)benzylidene-4-nitroaniline. J Fluoresc. 2017;27:2263–77.

    Article  CAS  PubMed  Google Scholar 

  26. Rai US, Singh M, Rai RN. Solid state synthesis, structural, physicochemical and optical properties of an inter-molecular compound: 2-hydroxy-1, 2-diphenylethanone-4-nitro-o-phenylenediamine system. J Solid State Chem. 2017;253:63–72.

    Article  CAS  Google Scholar 

  27. Singh M, et al. Solid–liquid equilibrium, thermal, and physicochemical studies on salicylamide–4-nitrophenol and 2-cyanoacetamide–4-aminoacetophenone organic eutectic systems. J Therm Anal Calorim. 2013;113(2):977–83.

    Article  CAS  Google Scholar 

  28. Calvaruso G, Ruggirello A, Turco V. Liveri. FT-IR investigation of the N-methylurea state in AOT reversed micelles. J Nanopart Res. 2002;4(3):239–46.

    Article  CAS  Google Scholar 

  29. Abkowicz-Bieńko AJ, et al. Theoretical infrared spectrum and revised assignment for para-nitrophenol. Density functional theory studies. Chem Phys. 1999;250(2):123–9.

    Article  Google Scholar 

  30. Samsonowicz M, et al. Experimental and theoretical IR, Raman, NMR spectra of 2-, 3-, and 4-nitrobenzoic acids. Int J Quantum Chem. 2007;107(2):480–94.

    Article  CAS  Google Scholar 

  31. Etter MC, et al. Hydrogen bond-directed co-crystallization and molecular recognition properties of diaryl ureas. J Am Chem Soc. 1990;112(23):8415–26.

    Article  CAS  Google Scholar 

  32. Ma G, et al. Thermal properties and reliability of eutectic mixture of stearic acid-acetamide as phase change material for latent heat storage. J Chem Thermodyn. 2017;106:178–86.

    Article  CAS  Google Scholar 

  33. Qazi SJS, Rennie AR, Cockcroft JK, et al. Use of wide-angle X-ray diffraction to measure shape and size of dispersed colloidal particles. J Colloid Interface Sci. 2009;338:105–10.

    Article  CAS  PubMed  Google Scholar 

  34. Singh M, et al. Synthesis, crystal growth and physicochemical studies on a novel organic inter-molecular compound; 3, 5-dinitrobenzoic acid and salicylamide system. J. Crystal Growth. 2015;419:114–22.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi, 221005, India

    Umesh Neupane, U. S. Rai & R. N. Rai

Authors
  1. Umesh Neupane
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. U. S. Rai
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. R. N. Rai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to R. N. Rai.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 936 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Neupane, U., Rai, U.S. & Rai, R.N. Thermal, physicochemical and spectroscopic studies on some novel organic complexes obtained by green synthesis. J Therm Anal Calorim 132, 1741–1752 (2018). https://doi.org/10.1007/s10973-018-7051-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-018-7051-z

Keywords

Search

Navigation