Synthesis, Growth and Characterization of Organic Nonlinear Optical Single Crystals of 4-Bromo-4’-Methyl Benzylidene Aniline


Organic nonlinear optical material of 4-bromo-4’-methyl benzylidene aniline (BMBA) was synthesized and single crystal of BMBA was grown by solvent evaporation method at room temperature using ethanol as solvent. The crystalline nature of the grown crystals was confirmed using powder X-ray diffraction studies. The crystals were also characterized by single crystal X-ray diffraction method and their lattice parameters were determined. Thermal properties of BMBA were evaluated with thermogravimetric, differential thermal and differential scanning calorimetric analyses. Fourier transform infrared and FT-Raman spectral studies were carried out on the BMBA material to confirm the synthesized compound. 1H and 13C-nuclear magnetic resonance spectral studies were recorded to elucidate the structure of the grown crystals. Fluorescence spectrum recorded shows a peak at 485 nm. UV-Vis-NIR spectral analysis shows transmittance of ~92% in the visible region. The mechanical stability was analyzed by Vickers microhardness tester and the work hardening coefficient of the grown crystal was calculated. Second harmonic generation efficiency of the grown crystal measured by Kurtz powder technique is ~1.8 times that of potassium dihydrogen orthophosphate.

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Jothi, L. , Babu, R. and Ramamurthi, K. (2014) Synthesis, Growth and Characterization of Organic Nonlinear Optical Single Crystals of 4-Bromo-4’-Methyl Benzylidene Aniline. Journal of Minerals and Materials Characterization and Engineering, 2, 308-318. doi: 10.4236/jmmce.2014.24036.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Prasad, P.N. and Williams, D.J. (1991) Introduction to Nonlinear Optical Effects in Organic Molecules and Polymers. Wiley, New York.
[2] Chemla, D.S. and Zyss, J. (1987) Nonlinear Optical Properties of Organic Molecules and Crystals. Academic Press, New York.
[3] Zhang, G., Liu, M., Xu, D., Yuan, D., Sheng, W. and Yao, J. (2000) Blue-Violet Light Second Harmonic Generation with CMTC Crystals. Journal of Materials Science Letters, 19, 1255-1257.
[4] Vijayan, N., Bhagavannarayana, G., Babu, R.R., Gopalakrishnan, R., Maurya, K.K. and Ramasamy, P. (2006) A Com- parative Study on Solution and Bridgman-Grown Single Crystals of Benzimidazole by High-Resolution X-Ray Diffractometry, Fourier Transform Infrared, Microhardness, Laser Damage Threshold and Second Harmonic Generation Measurements. Crystal Growth and Design, 6, 1542-1546.
[5] Srinivasan, P., Kanagasekaran, T. and Gopalakrishnan, R. (2008) A Highly Efficient Organic Nonlinear Optical Donor-Acceptor Single Crystal: L-Valinium Picrate. Crystal Growth and Design, 8, 2340-2345.
[6] Rai, R.N. and Lan, C.W. (2002) The Crystal Structure and Properties of a New Organic Nonlinear Optical Material. Journal of Materials Research, 17, 1588-1591.
[7] Kelker, H. and Scheurle, B. (2003) A Liquid Crystalline (Nematic) Phase with a Particularly Low Solidification Point. Angewandte Chemie International Edition in English, 8, 884-885.
[8] Hadjoudis, E., Vittorakis, M. and Maustakali-Mavridis, I. (1987) Photochromism and Thermochromism of Schiff Bases in the Solid State and in Rigid Glasses. Tetrahedron, 43, 1345-1360.
[9] Shepherd, E.E.A., Sherwood, J.N., Simpson, G.S. and Yoon, C.S. (1991) The Growth, Perfection and Properties of Organic Non-Linear Optical Materials 1. 4-Nitro-4-Methylbenzylidene Aniline. Journal of Crystal Growth, 113, 360- 370.
[10] Bailey, R.T., Bourhill, G., Cruickshank, F.R., Pugh, D., Sherwood, J.N. and Simpson, G.S. (1993) The Linear and Nonlinear Optical Properties of the Organic Nonlinear Material 4-Nitro-4-Methylbenzylidene Aniline. Journal of Applied Physics, 73, 1591-1597.
[11] Leela, S., Ramamuthi, K. and Bhagavannarayana, G. (2009) Synthesis, Growth, Spectral, Thermal, Mechanical and Optical Properties of 4-Chloro-4-Dimethylamino-Benzylidene Aniline: A Third Order Nonlinear Optical Material. Spectrochimica Acta Part A, 74, 78-83.
[12] Leela, S., Hema, R., Stoeckli-Evans, H., Ramamurthi, K. and Bhagavannarayanna, G. (2010) Design, Synthesis, Growth and Characterization of 4-Methoxy-4-Dimethylamino-Benzylidene Aniline (MDMABA): A Novel Third Order Nonlinear Optical Material. Spectrochimica Acta Part A, 77, 927-932.
[13] Subashini, A., Kumaravel, R., Leela, S., Stoeckli-Evans, H., Sastikumar, D. and Ramamurthi, K. (2011) Synthesis, Growth and Characterization of 4-Bromo-4-Chlorobenzylidene Aniline—A Novel Third Order Nonlinear Optical Material. Spectrochimica Acta Part A, 78, 935-941.
[14] Jothi, L., Vasuki, G., Ramesh Babu, R. and Ramamurthi, K. (2012) 4-Bromo-N-(4-Hydroxy Benzylidene) Aniline. Acta Crystallographica Section E, 68, o772.
[15] Udayalakshmi, K., Ramamurthi, K. and Ramasamy, P. (2006) Optical, Mechanical and Thermal Properties of p-Bromoacetanilide. Crystal Research and Technology, 41, 795-799.
[16] David, R.L. (1999-2000) CRC Handbook of Chemistry and Physics. 80th Edition, CRC Press, Boca Roton.
[17] Kemp, W. (1993) Organic Spectroscopy. 3rd Edition, ELBS, Macmillan.
[18] Kalsi, P. (1985) Spectroscopy of Organic Compounds. Wiley Eastern, New Delhi.
[19] Dani, V.R. (1995) Organic Spectroscopy. Tata McGraw-Hill, New Delhi.
[20] Vijayan, N., Ramesh Babu, R., Gunasekaran, M., Gopalakrishnan, R. and Ramasamy, P. (2003) Growth, Optical, Thermal and Mechanical Studies of Methyl 4-Hydrobenzoate Single Crystals. Journal of Crystal Growth, 256, 174-182.
[21] Willard, H.H., Merritt Jr., L.L., Dean, J.A. and Settle, F.A. (1986) Instrumental Methods of Analysis. 6th Edition, Wadworth Publishing Company, USA.
[22] Sangwal, K. (2000) On the Reverse Indentation Size Effect and Microhardness Measurement of Solids. Materials Chemistry and Physics, 63, 145-152.
[23] Onitch, E.M. (1956) The Present Status of Testing the Hardness of Materials. Microskopie, 95, 12-14.
[24] Kurtz, S.K. and Perry, T.T. (1968) A Powder Technique for the Evaluation of Nonlinear Optical Materials. Journal of Applied Physics, 39, 3798-3813.

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