Journal of Thermal Analysis and Calorimetry

, Volume 134, Issue 2, pp 1059–1070 | Cite as

2-Amino-6-methylpyridinium nitrophenolate nitrophenol

An organic multiple charge-transfer complex with large second harmonic generation for optoelectronics applications
  • B. Babu
  • J. Chandrasekaran
  • V. Jayaramakrishnan
  • Mon-Shu Ho
  • K. Thirupugalmani
  • S. Chandrasekar
  • R. Thirumurugan


Organic co-crystals fashioned with two or more different constituents through intermolecular non-covalent interactions (hydrogen and halogen bonds) gain cumulative research considerations as of their applications in ambipolar charge transport, nonlinear optics (NLO), light-driven actuator, liquid crystal material and electronics industry. In this contribution, charge-transfer (CT) interactions and the corresponding physicochemical and nonlinear properties of bulk organic, CT co-crystal of 2-amino-6-methylpyridinium nitrophenolate nitrophenol (2A6MPNN) were comprehensively investigated. CT crystals were fabricated by the facile solvent evaporation strategy and crystallized with an extensive hydrogen bonding network existed between the aromatic donor (D) and acceptor (A). The organic salt formation of phenol–pyridine co-crystal was investigated by using 1H NMR, 13C NMR and FTIR. More importantly, we show that the CT interactions in co-crystals are related to their molecular packing which eventually leads to distinct optoelectronic properties. The convincing evidence for multiple CT was found by UV–Vis spectral measurements, i.e., both π–π and n–π* interactions (between 4-nitrophenol and 2-amino-6-methylpyridine) are simultaneously present and additionally new feature band arises at 408 nm. Remarkably, upon photoexcitation at 374 nm in the solid state, CT displays an unusual emission around 572 nm, which is probably attributed for the shallow traps of the ion pairs, along with a usual phenolate-centered green emission. Thermal analysis was performed using TG/DTA/DSC and Modulated DSC studies. NLO response on CT powder (for diverse particle sizes) indicates a phase matchability and NLO coefficient about 1.8-fold larger than that of urea.


Organic Solution growth Nonlinear Thermal 



The authors are indebted to Prof. P.K. Das, Department of Inorganic and Physical Chemistry, IISc, Bangalore for the SHG measurements.

Supplementary material

10973_2018_7386_MOESM1_ESM.docx (120 kb)
Compositional and density measurement; 1H-NMR and 13C NMR spectrum figures (DOCX 119 kb)


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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  • B. Babu
    • 1
    • 2
  • J. Chandrasekaran
    • 3
  • V. Jayaramakrishnan
    • 4
  • Mon-Shu Ho
    • 1
    • 2
  • K. Thirupugalmani
    • 5
  • S. Chandrasekar
    • 1
    • 2
  • R. Thirumurugan
    • 6
  1. 1.Department of PhysicsNational Chung Hsing UniversityTaichung CityTaiwan
  2. 2.Innovation and Development Center of Sustainable Agriculture (IDCSA)National Chung Hsing UniversityTaichung CityTaiwan
  3. 3.Crystal Research Laboratory, Department of PhysicsSri Ramakrishna Mission Vidyalaya College of Arts and ScienceCoimbatoreIndia
  4. 4.Centro de Investigaciones en OpticaLeónMexico
  5. 5.Crystal Research Laboratory, Department of PhysicsERK Arts and Science CollegeDharmapuriIndia
  6. 6.Department of Physics, School of PhysicsMadurai Kamaraj UniversityMaduraiIndia

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