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Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 116 (2013) 143147

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Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy

journal homepage: www.elsevier.com/locate/saa

Synthesis, crystal growth and spectroscopic investigation of second order organic nonlinear optical single crystal: 2-Chloro-N-[4(dimethylamino)benzylidene]aniline
R.K. Balachandar, S. Kalainathan
Centre for Crystal Growth, SAS, VIT University, Vellore 632 014, Tamil Nadu, India

h i g h l i g h t s
 First time single crystal of 2Cl4DBA

g r a p h i c a l a b s t r a c t

was grown by slow evaporation technique from synthesized compound.  NMR, FTIR spectral analysis and XRD technique were used to conrm the product formation.  Good thermal stability of the grown crystal is up to 135 C.  SHG efciency of title crystal was more than that of standard KDP and urea material.

a r t i c l e

i n f o

a b s t r a c t
Organic nonlinear optical (NLO) crystal 2-chloro-N-[4-(dimethylamino)benzylidene]aniline (2Cl4DBA) was synthesized and grown by restricted slow evaporation technique at room temperature using acetone as solvent with good degree of transparency. The lattice parameters were determined and found to be noncentrosymmetric orthorhombic system by single crystal X-ray diffraction. The crystalline nature of the synthesized material was recorded by the powder X-ray diffraction pattern. Molecular structure of the grown crystal was investigated by 1H and 13C NMR and functional groups were identied by FTIR spectrum analysis. The optical absorbance of the grown crystal was ascertained by recording UVVisible spectrum. Thermal and physiochemical stability of the grown material was investigated by TG/DTA analysis. SHG efciency was determined by KurtzPerry Powder SHG technique and found to be 4.2 and 1.54 times greater that of standard KDP and urea crystals respectively. 2013 Elsevier B.V. All rights reserved.

Article history: Received 12 February 2013 Received in revised form 28 June 2013 Accepted 16 July 2013 Available online 24 July 2013 Keywords: Slow evaporation technique Nonlinear optics X-ray diffraction NMR Organic compounds

Introduction Organic nonlinear optical materials (NLO) play a major role in nonlinear optics for the fast processing of information and for data storage applications. Organic NLO materials have been investigated due to their potentially large nonlinearities and rapid response in electro-optic effect compared to inorganic NLO materials, large numbers of molecules were available for investigation. The optical
Corresponding author. Tel.: +91 416 2202350; fax: +91 416 2243092.
E-mail address: kalainathan@yahoo.com (S. Kalainathan). 1386-1425/$ - see front matter 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.saa.2013.07.021

nonlinearity of the aromatic organic molecules were enhanced when the molecule has one donor at the one end and one acceptor group bonded at the other end of the conjugated system of the molecule. An organic crystal with delocalized p-electrons usually displays a large NLO response which makes it attractive for applications in integrated optics [13]. Most of the organic crystals are composed of aromatic molecules that are substituted with electron donors and acceptors which exhibit intramolecular charge transfer. In the present investigation, the synthesis of the Schiff base compound, for the rst time we report crystal growth of the title compound and its detailed molecular and structural conrma-


R.K. Balachandar, S. Kalainathan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 116 (2013) 143147

tion by spectroscopic techniques. Thermal and second harmonic generation efciency of 2-chloro-N-[4-(dimethylamino)benzylidene]aniline single crystals have been studied.

Results and discussion Single crystal X-ray diffraction Single crystal data collection analysis was performed by using diffractometer-MACH3 from EnrafNonius and CCD detector based-SMART APEX from Bruker-Nonius Axs. The single crystal XRD study reveals that the crystal belongs to non-centrosymmetric orthorhombic system, satisfying one of the basic and essential requirements for the SHG activity of the material, the space group P212121 with the lattice parameter a = 7.6864 , b = 12.1654 , c = 13.9688 and V = 1306.138 , which is in good agreement with those of reported values [4]. Powder X-ray diffraction Powder X-ray diffraction patterns of nely crushed powder of 2Cl4DBA crystal was scanned in the 2h values ranging from 10 to 80 and the powder X-ray diffraction pattern were recorded with Bruker, D8 Advance model, Cu Ka radiation (k = 1.5406 ). The powder XRD Prominent peaks of title crystal (h kl) values were indexed using POWDER X software program and are shown in Fig. 1.

Experimental procedure Material synthesis The 2Cl4DBA was synthesized by the condensation reaction between p-aminobenzaldehyde (10 mmol, 1.491 g, aldehyde) and 2-chloroaniline (10 mmol, 1.054 ml, primary amine) in an equimolar amount (1:1) dissolving in ethanol. Three drops of glacial acetic acid were added as catalyst. The prepared material was taken in a round bottom ask and reuxed for 8 h. The yield material was Schiff base compounds containing imine groups (AHC@NA). Then the reaction mixture was allowed to cool to room temperature and salt formation occurred at the bottom of the ask as light yellow microcrystalline powder. Using thin layer chromatography (TLC) the product was conrmed as a single compound and the solid product was separated using Whatman lter paper by ltering the solution and kept for dryness (yield about 77%). Purity of the synthesized compound was further increased by three times recrystallization in the solvent acetone and the reaction mechanism is shown in scheme below (see Scheme 1).

H and


C NMR spectral analyses

Crystal growth The puried material was dissolved in the solvent acetone and stirred continuously for 5 h using magnetic stirrer and the prepared saturated solution was ltered and covered tightly with aluminum foil kept undisturbed at room temperature for controlled slow evaporation. Natural evaporation of the acetone induces the spontaneous nucleation in the solution and tiny single crystals of optically transparent good quality have been harvested after 7 days. Grown crystals were subjected to various characterization studies like XRD, NMR, FTIR, UV Visible, TG/DTA and SHG. (Supplementary Fig. S1) is shown the grown crystal of 2Cl4DBA.

In the present investigation, 1H and 13C NMR spectrum of the puried 2C4DBA sample was recorded using Bruker 400 MHz instrument in deuterated chloroform with tetramethylsilane (TMS) as the internal standard. The structure of 2Cl4DBA containing different types of protons show different peaks as expected at different chemical shift positions from the different environment of the proton [5]. The protons in the aldehyde rings can see each other as aligned (parallel) or opposed (anti-parallel) and come to resonance twice. The proton pairs are chemically equivalent by virtue of the symmetry within the molecule and have same electronic environment. Thus, proton in the aldehyde ring appears as doublet because their signals are indistinguishable, d (7.853, 7.831) ppm and d (6.774, 6.752) ppm gives two doublets respectively. The imine protons (AHC@NA) have no neighbor proton and it should

Cl NH 2

H 3C N H 3C C

Add 3drops of Glacial acetic acid and reflux for 8hours

H 3C N H 3C C H

H 2O

Scheme 1. Reaction mechanism of 2Cl4DBA.

R.K. Balachandar, S. Kalainathan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 116 (2013) 143147


three-line signal (d 7677) from the CDCl3 solvent corresponds to the single carbon atom; it appears as a triplet because of an interaction with the deuterium atom. Rest of all the peaks corresponds to the aromatic carbons which fall on the aromatic region from (d 111.035152.814). Thus the molecular structure of the title compound is conrmed from the proton NMR and carbon NMR spectrum. 13C NMR spectrum of title material is shown in (Supplementary Fig. S3). FTIR spectral analysis FTIR spectrum was recorded for the crushed powder of the crystal using Shimadzu FTIR spectrophotometer. The spectra were recorded by KBr pellet technique between the range 400 cm1 and 4000 cm1 shown in Fig. 2. Benzylidene anilines display their C@N stretching as a band at 1600 cm1. The band obtained at 1598 cm1 is a proof for the formation of imine group (C = N) as a result of the condensation reaction between aldehyde and amine [7]. The expected bending vibrations of CAX bond are strong for CACl stretching is 600800 cm1. In the present case, the absorption is noticed at 759 cm1. C-H stretching absorptions are weak absorptions expected around 2924 cm1. C@C stretching absorption is conrmed from the band at 1502 cm1. An out-of-plane CAH deformation band is a characteristic of aromatic ring with ortho-di-substitution. It is conrmed from the band at 750 cm1. It is evidenced from the CAH deformation vibration at 750 cm1 [8]. Absence of characteristic aldehyde bands at 2720 cm1 and 2820 cm1 indicates that there is no aldehyde group in the nal product. FTIR spectrum does not show any signal corresponding to aldehyde group present in the reactants. From the above observations the presence of the specic groups are conrmed. UVvisible spectral analysis The optical absorption spectrum of the grown crystal was recorded using Elico SL218 Double beam UVvisible spectropho-

Fig. 1. Powder XRD pattern of the grown crystal.

appear as a singlet. The singlet signal at d 8.261 ppm corresponds to the proton of imine group which conrms the formation of the Schiff base compound [6]. The d values for the protons of (ACH3)2 group attached to-N-Aromatic radicals are expected at 3.082 ppm. The singlet signal at d 3.082 ppm denotes protons of methyl group. Aniline ring had four protons, out of the four protons two of hydrogen atoms were neighbors to two H-atoms thus it forms a two triplets (d 7.125, 7.283 ppm) and the remaining two proton forms a doublets with each one H atom as neighbor (d 7.056, 7.452 ppm) this is due to the chlorine atom is attached to the ortho position of the aromatic aniline ring. 1H NMR spectrum of the grown material is shown in (Supplementary Fig. S2). From 13C NMR of the title compound, the assignment of the each signal to a unique carbon environment in the molecule is also identied. Each carbon atom at different positions produces a different signal. The shift (d 161.591) is due to the imine group carbon atom which conrms the formation of the Schiff base compound. The signal (d 40.170) is due to the methyl carbon atom and the

Fig. 2. FTIR spectrum of the grown crystal.


R.K. Balachandar, S. Kalainathan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 116 (2013) 143147

observed that the material is stable up to 234 C and weight loss of the material starts on further heating the sample. 85% of huge weight loss is observed between the temperature 234oC and 317oC due to the decomposition of the imine molecule and remaining 15% as carbon residue which is present in the material. From the above observation, it is clear that there is no weight loss between 100 C and 200 C which attributes that there is no inclusion of water molecules present in the crystal lattice and also no weight loss before the melting point, which indicates that the material is moisture-free and stable up to 234 C. From the DTA analysis the two sharp endothermic peaks were observed at 135 C and 321 C, the rst one corresponds to the melting point of the material, sharpness indicates the good crystalline nature and purity of the synthesized material and the second is corresponds to the complete decomposition of title compound which may release volatile gases present in the material [9]. Other than the solidliquid transformation from the melting point onwards, no other phase transformations are noticed in the DTA curve.

Second harmonic generation measurement

Fig. 3. UVvisible absorbance spectrum of the grown crystal.

tometer in the wavelength range of 1901100 nm at room temperature. A sample of 1.7 mm thickness was used for measurement without polishing the crystal surface. The recorded UVvisible spectrum is shown in Fig. 3. It is observed that cut off wavelength is at 434 nm. The crystal has low absorption starts in the visible and completely in the NIR region. The low absorbance in the region from 434 nm to 1100 nm enables very good optical transmission of the second harmonic frequencies of Nd:YAG laser.

SHG conversion efciency measurement was carried out using Kurtz and Perry technique [10]. A Q-switched Nd:YAG laser beam of wavelength 1064 nm with input beam energy 3.8 mJ/pulse and pulse width 10 ns with a repetition rate of 10 Hz was used. The grown single crystal was powdered with a uniform particle size and tightly packed in a micro-capillary of uniform bore and exposed to the laser radiation. The bright green light emission (k = 532 nm) was observed which indicates the SHG behavior of the title material. The relative SHG efciency of the title crystal (42 mV) is nearly 4.2 and 1.54 times that of KDP (10 mV) and urea (27.2 mV) respectively.

Thermal analysis The thermal stability of the grown crystal was measured by thermo gravimetric analysis (TGA) and Differential thermal analysis (DTA) simultaneously from room temperature to 500 C at the heating rate of 10 K/min, under nitrogen atmosphere using Netzsch STA 409 PL Luxx as shown in Fig. 4. From TG analysis it is Conclusion The organic NLO material 2-chloro-N-[4-(dimethylamino)benzylidene]aniline was successfully synthesized and grown the single crystal from the acetone by restricted slow evaporation technique. Single crystal X-ray diffraction has been carried out to nd the unit cell parameter and the crystalline nature of the synthesized material was analyzed by powder XRD pattern. Conrmation of the molecular and structural was done by FTIR and NMR spectral analysis. UV visible spectrum of the grown crystal shows low absorbance with cutoff 434 nm in the near visible region and entire near IR region. A thermal property of the grown material studied by TG/DTA analysis and melting point of the material was found to be 135 C and the materials was stable up to 235 C. The SHG relative efciency was found to be more efciency 4.2 times and 1.5 times than that of standard KDP and urea as a reference material. Thus the characterization conrms the suitability of the grown crystal for NLO applications.

Acknowledgements The authors express thank to R. Lakshmi sundaram, Sri Ramachandra University for helping in the NMR spectral analysis. The authors also express thanks to VIT University for their constant encouragement and nancial support.

Appendix A. Supplementary material Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.saa.2013.07.021.

Fig. 4. TG/DTA curve of the grown crystal.

R.K. Balachandar, S. Kalainathan / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 116 (2013) 143147


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