Abstract
L-threoninium p-toluenesulfonate monohydrate (LTPTM) (IUPAC name: 1-carboxy-2-hydroxypropan-1-aminium 4-methylbenzenesulfonate monohydrate), a new organic nonlinear optical (NLO) crystal, is grown by solution growth method at room temperature. It crystallizes in monoclinic crystal system with noncentrosymmetric space group P21. Presence of NH3+ and SO3− vibrations in IR and Raman spectra confirms the formation of LTPTM molecule. The 1H and 13C nuclear magnetic resonance (NMR) spectra establish the molecular structure. In the 1H–NMR spectrum of LTPTM, the chemical shift corresponding to H-SO3 (6.57 ppm) of p-toluenesulfonic acid monohydrate is absent. This is due to the fact that the hydrogen in H–SO3 is released and combines with the amine group of l-threonine. This ensures the formation of LTPTM molecule. The O5-H5A…O3 intermolecular interaction is also established by the observed upfield shift of COOH group in LTPTM molecule. The crystal is thermally stable up to 73 °C. LTPTM is transparent from 235 to 1100 nm. The second harmonic generation (SHG) conversion efficiency of LTPTM is 0.77 times that of KDP. Third order nonlinear optical susceptibility (χ(3)) of the title crystal is 1.3035 × 10−7 esu which is higher than some reported NLO crystals.
Similar content being viewed by others
References
Arunkumar, A., Ramasamy, P.: Bulk single crystals of ammonium acid phthalate grown by the Sankaranarayanan–Ramasamy method for optical limiting applications. J. Cryst. Growth 401, 195–199 (2014)
Babu, G.A., Ramasamy, R.P., Ramasamy, P., Kumar, V.K.: Synthesis, crystal growth, and characterization of an organic nonlinear optical donor-π-acceptor single crystal: 2-amino-5-nitropyridinium-toluenesulfonate. Cryst. Growth Des. 9(7), 3333–3337 (2009)
Bhat, M.N., Dharmaprakash, S.M.: Growth of nonlinear optical γ-glycine crystals. J. Cryst. Growth 236, 376–380 (2002)
Brown, W.H., Foote, C.S., Iverson, B.L., Anslyn, E., Chemistry, O.: Organic Chemistry, 5th edn, p. 499. Brooks/Cole Cengage Learning, USA (2009)
Chemla, D.S., Zyss, J. (eds.): Nonlinear Optical Properties of Organic molecules and Crystals. Academic Press, New York (1987)
Dean, J.A.: Analytical Chemistry Handbook. McGraw-Hill, New York (1995)
Dmitriev, V.G., Gurzadyan, G.G., Nicogosyan, D.N.: Handbook of Nonlinear Optical Crystals. Springer, New York (1999)
Gupte, S.S., Marcano, A., Pradhan, R.D., Desai, C.F., Melikechi, N.: Pump-probe thermal lens near-infrared spectroscopy and Z-scan study of zinc (tris) thiourea sulfate. Appl. Phys. 89, 4939–4943 (2001)
Hann, R.A., Bloor, D. (eds.): Organic Materials for Nonlinear Optics, (Spl. Pub No. 69). The Royal Society of Chemistry, Burlington (1989)
http://sdbs.db.aist.go.jp/sdbs/cgi-bin/cre_frame_disp.cgi?spectrum_type=cnmr&sdbsno=1079
http://sdbs.db.aist.go.jp/sdbs/cgi-bin/cre_frame_disp.cgi?spectrum_type=hnmr&sdbsno=1635
http://sdbs.db.aist.go.jp/sdbs/cgi-bin/cre_frame_disp.cgi?spectrum_type=hnmr&sdbsno=5795
http://sdbs.db.aist.go.jp/sdbs/cgi-bin/cre_frame_disp.cgi?spectrum_type=cnmr&sdbsno=5795
KrishnaKumar, M., Sudhahar, S., Pandi, P., Bhagavannarayana, G., MohanKumar, R.: Studies of the structural and third-order nonlinear optical properties of solution grown 4-hydroxy-3-methoxy-4′-N′-methylstilbazolium tosylate monohydrate crystals. Opt Mater 36, 988–995 (2014)
Kurtz, S.K., Perry, T.T.: A powder technique for the evaluation of nonlinear optical materials. J. Appl. Phys. 39, 3798–3813 (1968)
Li, F.Q., Zong, N., Zhang, F.F., Yang, J., Yang, F., Peng, Q.J., Cui, D.F., Zhang, J.Y., Wang, X.Y., Chen, C.T., Xu, Z.Y.: Investigation of third-order optical nonlinearity in KBe2BO3F2 crystal by Z-scan. Appl. Phys. B 108, 301–305 (2012)
Masilamani, S., MohamedMusthafa, A., Krishnamurthi, P.: Synthesis, growth and characterisation of a semiorganic nonlinear optical material: L-threonine cadmium chloride single crystals. Arab. J. Chem. 10, S3962–S3966 (2017)
Newman, P.R., Warren, L.F., Cunningham, P., Chang, T.Y., Cooper, D.E., Burdge, G.L., Polok- Dingels, P., Lowe-Ma, C.K., Mater. Res. Soc. Symp. Proc., 173 (1990), p. 557
Monaco, S.B., Davis, L.E., Velsko, S.P., Wong, F.T., Eimerl, D.: Synthesis and characterization of chemical analogs of L-arginine phosphate. J. Cryst. Growth 85, 252–255 (1987)
Nilapwar, S.M., Nardelli, M., Westerhoff, H.V., Verma, M., Spectroscopy, A.: Chapter 4, 60–64 (2011)
Pawlukojc, A., Leciejewicz, J., Tomkinson, J., Parker, S.F.: Neutron scattering, infra red, Raman spectroscopy and ab initio study of l-threonine. Spectrochim. Acta A 57, 2513–2523 (2001)
Pejov, L., Ristova, M., Soptrajanov, B.: Quantum chemical study of p-toluenesulfonic acid, p-toluenesulfonate anion and the water–p-toluenesulfonic acid complex. Comparison with experimental spectroscopic data. Spectrochim. Acta A 79, 27–34 (2011)
Prabu, P., Thiruvalluvar, A., Ramachandra Raja, C.: 1-Carboxy-2-hydroxypropan-1-aminium 4-methylbenzenesulfonate monohydrate. IUCrData 3, x171848 (2018)
Razzetti, C., Ardoino, M., Zanotti, L., Zha, M., Paorici, C.: Solution growth and characterisation of L‐alanine single crystals. Cryst. Res. Technol. 37, 456–465 (2002)
Ristova, M., Pejov, L., Zugic, M., Soptrajanov, B.: Experimental IR, Raman and ab initio molecular orbital study of the 4-methylbenzenesulfonate anion. J. Mol. Struct. 482–483, 647–651 (1999)
Selvakumar, E., Anandhababu, G., Ramasamy, P., Devi, T.U., Meenakshi, R., Chandramohan, A.: Synthesis, growth, structure and spectroscopic characterization of a new organic nonlinear optical hydrogen bonding complex crystal: 3-Carboxyl anilinium p-toluene sulfonate. Spectrochim Acta A Mol Biomol Spectr 125, 114–119 (2014)
Shettigar, S., Umesh, G., Chandrasekaran, K., Kalluraya, B.: Third order nonlinear optical properties and two photon absorption in newly synthesized phenyl sydnone doped polymer. Synth. Met. 157, 142–146 (2007)
Subhashini, R., Sathya, D., Sivashankar, V., LathaMageshwari, P.S., Arjunan, S.: Growth and characterization of Bis (l-threonine) copper (II) monohydrate single crystals: a semiorganic second order nonlinear optical material. Opt Mater 62, 357–365 (2016)
Suresh, M., Bahadur, S.A., Athimoolam, S.: Investigations on spectroscopic, optical, thermal and dielectric properties of a new NLO material: L-Histidinium p-toluenesulfonate [LHPT]. Optik 126, 5452–5455 (2015)
Suresh, M., Bahadur, S.A., Athimoolam, S.: Structural and solid state properties of L-leucinium p-toluenesulfonate monohydrate: an amino acid tosylate NLO crystal. J. Mater. Sci.: Mater. Electron. 28(1), 661–672 (2016a)
Suresh, M., Bahadur, S.A., Athimoolam, S.: Synthesis, growth and characterization of a new hydrogen bonded organic tosylate crystal: L-alaninium p-toluenesulfonate for second order nonlinear optical applications. J. Mater. Sci. Mater. Electron. 27(5), 4578–4589 (2016b)
Suresh, M., Bahadur, S.A., Athimoolam, S.: Synthesis, growth, structural, spectral, thermal and microhardness studies of a new hydrogen bonded organic nonlinear optical material: L–valinium p–toluenesulfonate monohydrate (LVPT). J. Mol. Struct. 1112, 71–80 (2016c)
Suresh, M., Bahadur, S.A., Athimoolam, S.: Structural and solid state properties of L-leucinium p-toluenesulfonate monohydrate: an amino acid tosylate NLO crystal. J. Mater. Sci. Mater. Electron. 28, 661–672 (2017)
Vediyappan, S., Arumugam, R., Pichan, K., Kasthuri, R., Pandian, M.S., Perumal, R.: Crystal growth and characterization of semi-organic 2-amino-5-nitropyridinium bromide (2A5NPBr) single crystals for third-order nonlinear optical (NLO) applications. Appl. Phys. A 123, 780–795 (2017)
Viju, G., Mariappan, L., Jose, M., JeromeDas, S.: Investigation on the growth, optical and thermal studies of a novel organic nonlinear optical crystal: L-Threonine diformate (LTDF). Optik 125(20), 5926–5928 (2014)
Wang, D., Li, T., Wang, S., Wang, J., Wang, Z., Xu, X., Zhang, F.: Study on nonlinear refractive properties of KDP and DKDP crystals. RSC Adv. 6, 14490–14495 (2016)
Wong, M.S., Bosshard, C., Pan, F., Gunter, P.: Non‐classical donor–acceptor chromophores for second order nonlinear optics. Adv. Mater. 8, 677–680 (1996)
Zhou, Y.S., Wang, E.B., Peng, J.: Synthesis and the third-order optical nonlinearities of two novel charge-transfer complexes of a heteropoly blue type (C9H7NO)4H7PMo12O40 3H2O (C9H7NO = quinolin-8-ol) and (phen) 3H7PMo12O40 CH3CN·H2O (phen = 1, 10-phenanthroline). Polyhedron 18, 1419–1423 (1999)
Acknowledgements
The author C.R gratefully acknowledges the Council of Scientific and Industrial Research (CSIR), New Delhi for their financial support (Scheme number: 03(1301)/13/EMR II). The authors thank the authorities of Sophisticated Analytical Instrument Facility (SAIF), IIT, Chennai, India for single crystal X-ray data collection. The authors are thankful to SASTRA University, Thanjavur, for having provided TG–DTA, UV–Vis-NIR, FT-IR and NMR spectral facilities. The authors also thank Prof. P.K. Das, Indian Institute of Science (IISC), Bangalore, India for having supported us with laser facilities towards SHG measurements. The authors are grateful to Professor Dr. D. Sasti Kumar, Department of Physics, NIT, Tiruchirappalli for having provided Z-scan facility. We also thank Dr. V. Ramanathan of SASTRA University for the Raman spectrum which was recorded in his lab for having used the Raman spectrometer purchased from the SERB grant SB/FT/CS-007/2013 of the DST.
Author information
Authors and Affiliations
Corresponding author
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
About this article
Cite this article
Prabu, P., Aarthi, R. & Ramachandra Raja, C. Growth and characterization studies on L-threoninium p-toluenesulfonate monohydrate crystal. Opt Quant Electron 51, 143 (2019). https://doi.org/10.1007/s11082-019-1862-4
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11082-019-1862-4