Crystal growth and characterization of piperazinium p-chlorobenzoate ...

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May 22, 2018 - and light modulation and optical switching etc (Sankar, G. U. (2007), Moorthy ... possess carbon – carbon bonds (Sankar, G. U., (2018)), carbon ...
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Vol. 14, 2018 ARTICLE

Science DISCOVERY

ISSN 2278–5485 EISSN 2278–5477

Crystal growth and characterization of piperazinium p-chlorobenzoate Vallikkodi M☼, Sudhahar S Department of Physics, Alagappa University, Karaikudi- 630 004, India ☼

Corresponding author:

Department of Physics, Alagappa University, Karaikudi- 630 004, India E-Mail: [email protected] Article History Received: 13 April 2018 Accepted: 22 May 2018 Published: May 2018 Citation Vallikkodi M, Sudhahar S. Crystal growth and characterization of piperazinium p-chlorobenzoate. Discovery Science, 2018, 14, 28-35 Publication License This work is licensed under a Creative Commons Attribution 4.0 International License. General Note Article is recommended to print as color version in recycled paper. Save Trees, Save Nature.

ABSTRACT The nonlinear optical properties of piperazinium p-chlorobenzoate (PCP) crystal were successfully grown with the help of temperature gradient method. The good quality of PCP single crystal is formed. The PCP is characterized with the help of X-ray diffraction (XRD), Fourier transform infrared (FTIR) measurement, photoluminescence (PL), Raman spectroscopy, ultra violet visible spectroscopy (UV) and finally etching analysis was done.

1. INTRODUCTION In recent years, organic materials which are used in the potential application such as frequency conversion, optical signal processing, and light modulation and optical switching etc (Sankar, G. U. (2007), Moorthy, C. G (2017). Sankar, G., (2016)) Organic compounds © 2018 Discovery Publication. All Rights Reserved. www.discoveryjournals.org

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Key words: Piperazinium p-chlorobenzoate , Non linear optical crystal , Slow evaporation method.

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ANALYSIS

possess carbon – carbon bonds (Sankar, G. U., (2018)), carbon – hydrogen bonds as well as covalent bonds between carbon and oxygen and nitrogen. It also has posses the strong nonlinear optical properties (Boyd, R. W. 2003). The most of the applications were made by using the artificial crystals like Piperazinium p-chlorobenzoate. The optical industry, electronic industry and optoelectronics in their applications the crystals are obtained the important role (Boyd, R. W. 2003). In this paper, the two organic compounds are mixed with the homogeneous process. The non linear optical single crystal of PCP is formed by the slow evaporation solution growth method and characterization and results of PCP crystal is obtained by using single crystal XRD, powder XRD, FTIR, Raman, PL, Etching and UV.

2. MATERIALS AND METHODS The piperazinium p-chlorobenzoate single crystal was prepared in the room temperature by slow evaporation solution growth method using as an acetone solvent. The precursor’s materials of piperazine (98%) and p-chlorobenzoic acid (99%) were taken in the equimolar ratio of 1:1 for the synthesis process is shown in figure 1. The p-chlorobenzoic acid was first dissolved in the solvent of acetone, after complete dissolved acid material and then the base compound of piperazine was added little by little with the acid solution (Zhu, Q., 2012). The solution is allowed to get a homogenous mixture by continuously stirring for 8 hours using the temperature control magnetic stirrer in the room temperature circumstances. After attaining the homogenous saturated state the solution was filtered using the whatman filter paper which is having the fine holes in the range of 110 m and the filtered solution was covered with the perforated sheet having the fine holes for the evaporation and it was kept at the room temperature without disturbance. After 2 successive recrystallization process the good quality PCP crystal was harvested with in the span of 56 days is shown in figure 2 (Mahalingam, Vallikkodi., 2018).

O

O

HN

HN Cl

Cl NH2+

NH HO

PIPERAZINE

P CHLOROBENZOIC ACID

-O

PIPERAZINIUM P CHLOROBENZOATE

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Figure 1 Synthesis scheme of piperazinium p-chlorobenzoate

Figure 2 Grown crystal of piperazinium p-chlorobenzoate © 2018 Discovery Publication. All Rights Reserved. www.discoveryjournals.org

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3. RESULT AND DISCUSSION XRD Analysis (i) The single crystal X-ray diffraction analysis is the powerful tool for determination of the structure of the crystal. The cell 3

parameters of the PCP is found to be a =14.91 Å, b = 6.326 Å, c = 6.310 Å, α =90,  =94.948, γ =90 and volume V = 592.99 Å . The PCP crystal belongs to the monoclinic crystal system with P21/n space group, thus satisfying one of the basic and essential requirements for NLO materials. The structural parameters of the PCP crystal were listed in the table 1. Table 1 PCP crystal Crystal property

Piperazinium P-chlorobenzoate +



Empirical formula

C4H11N2 • C7H4ClO2

Crystal system

Monoclinic

Space group

P21/n

Unit cell parameters

a = 14.91 Å, b =6.326 Å, c = 6.310 Å, α = 90,  = 94.948, γ = 90 3

Volume of the unit cell

V = 748 Å

Radiation wavelength

 = 0.71073 Å

(ii) The crystalline nature of the piperazinium p-chlorobenzoate crystal was characterized by Powder x-ray diffraction analysis to reveal crystalline perfection of the compound. The x-ray diffraction spectrum of PCP was recorded using the X’pert PRO powder diffractometer with CuKα radiation having the wavelength of  = 1.5406 Å. The sample was scanned from the range of 10 to 80 at the rate of 2/minute. The recorded powder x-ray diffraction spectrum is shown in Figure 3. The presence of sharp and well defined peaks confirms the good crystalline nature of Piperazinium p-chlorobenzoate crystal and the corresponding peaks were indexed. The sharp intense peak was found at 22.4°with the crystal faces of (310). The sharp intense peaks are shown in the table 2. Table 2 Peaks of XRD FWHM Left [°2Th.]

d-spacing [Å]

14.7069

77.37

0.1476

6.02343

7.48

16.6224

176.25

0.1968

5.33337

17.04

18.1809

100.49

0.1476

4.87954

9.72

19.7484

80.99

0.1476

4.49565

7.83

20.1696

446.77

0.1968

4.40271

43.20

21.7896

430.82

0.1476

4.07890

41.66

22.4797

1034.23

0.1968

3.95521

100.00

25.4805

221.98

0.1476

3.49581

21.46

27.7228

123.40

0.1476

3.21795

11.93

29.2866

319.77

0.1476

3.04959

30.92

30.5905

119.80

0.2460

2.92250

11.58

31.4813

141.33

0.1968

2.84182

13.67

33.1687

115.07

0.1968

2.70100

11.13

33.5828

39.46

0.1476

2.66864

3.82

34.4488

46.07

0.1476

2.60351

4.45

35.3384

32.82

0.1476

2.53998

3.17

36.9673

132.69

0.3444

2.43171

12.83

38.6006

47.94

0.1476

2.33250

4.64

39.8114

123.66

0.1476

2.26431

11.96

43.1903

25.59

0.2952

2.09468

2.47

45.8773

23.94

0.2952

1.97806

2.31

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Rel. Int. [%]

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Height [cts]

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Pos. [°2Th.]

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48.8818

32.39

0.1968

1.86327

3.13

49.8526

25.25

0.2952

1.82924

2.44

51.2820

51.57

0.1968

1.78156

4.99

53.1836

54.02

0.2460

1.72226

5.22

56.5272

17.10

0.3936

1.62807

1.65

60.3542

29.38

0.1476

1.53367

2.84

77.7309

13.80

0.5904

1.22860

1.33

Figure 3 Powder XRD pattern of PCP crystal FTIR Analysis The FTIR spectrum was recorded to understand the chemical bonding and it provides useful information regarding the molecular structure of the compound. The KBr pellet technique was used to analyze the sample. FTIR spectrum was taken for the powdered sample in the wavelength range 4000-400 cm

-1

using 380 FTIR Spectrophotometer having the resolution of 0.5 cm

-1

and the

spectrum of FTIR is shown in Figure 4. The observed FTIR is summarized in table 3. Table 3 FTIR frequency assignments of PCP compound FTIR Experimental value

Assignments

Water

3700 – 3100

3246.55

OH stretch

Alcohols

1200 -1000

1094.15

C-O stretch

Acid chloride

1810 – 1775

1790.95

C=O stretch

Acid chloride

730 – 550

598.87

C-CL stretch

Carboxyl

1320 – 1210

1273.76

C-O stretch

Alkanes

~1465

1469.42

CH2 bend

Alkanes

~720

723.71

CH2 bending 4 more

Aromatics

3020 - 3000

3005.72

C-H stretch

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Theoretical value

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Functional groups

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ANALYSIS Aromatics

1600 – 1505

1589.90

C-C stretching in ring

Amines

3500 – 3300

3442.26

N-H stretch

Amines

1200 – 1025

1094.15

C-N (stretch)Alkyl

Figure 4 FTIR spectrum of PCP Raman Analysis -1

Laser Raman spectrum was taken for the powdered sample in the wavelength range 4000-400 cm using STR 500 mm focal length laser Raman spectrometer and the Raman spectrum is shown in the figure 5. Raman bands along with their vibrational assignments are summarized in table 4. Table 4 Raman frequency assignments of PCP compound

Water

3700 – 3100

----

OH stretch

Alcohols

1200 -1000

----

C-O stretch

Acid chloride

1810 – 1775

1781

C=O stretch

Acid chloride

730 – 550

----

C-CL stretch

Carboxyl

1320 – 1210

----

C-O stretch

Alkanes

~1465

1464

CH2 bend

Alkanes

~720

----

CH2 bending 4 more

Aromatics

3020 - 3000

----

C-H stretch

Aromatics

1600 – 1505

1597

C-C stretching in ring

Experimental value

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Assignments

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Theoretical value

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Laser Ramam

Functional groups

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Amines

3500 – 3300

3355

N-H stretch

Amines

1200 – 1025

1090

C-N (stretch)Alkyl

Figure 5 Laser Raman spectrum of PCP UV-Visible optical Absorption spectral analysis The optical absorption spectral analysis of the grown PCP crystal was carried out using Perkin Elmer Lambda35 spectrometer between 250 and 800 nm. The absorption & transmittance spectrum of the as grown PCP crystal is shown in the Figure 6. The UV cut off wavelength of the crystal was found to be at 280 nm. The absence of absorption in the visible region suggests that the crystal possess the good nonlinear optical property.

Photo luminescence spectroscopy is a non destructive method for finding out the electronic structure and optical behavior. The Photoluminescence spectrum of the grown PCP was recorded in the wavelength region between 300 nm and 550 nm using RF-5301 spectrophotometer. The PL spectrum (Figure 7) of PCP grown crystal is excited at 538 nm. From the PL spectrum, one high and one © 2018 Discovery Publication. All Rights Reserved. www.discoveryjournals.org

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Photoluminescence studies

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Figure 6 UV-Visible absorption & transmittance spectrum of PCP

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medium intensities green emission peaks and one medium intensity yellow emission peak was observed at 491 nm, 538 nm and 594 nm respectively. The sharp high intensity caused because of the similar transition occurring at the various energy levels within the band gap.

Figure 7 Photoluminescence spectrum of PCP Etching Studies

4. CONCLUSION The piperazinium p-chlorobenzoate crystal was successfully grown and characterized. The XRD pattern confirms the properties of NLO and the Raman and FTIR confirm all the functional groups. The UV and PL show the Optical properties. Thus, a good NLO crystal was successfully formed for LASER applications.

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Application of Ultraviolet LED. Computing.

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4. Boyd, R. W. (2003). Nonlinear optics. Academic press. 5. Zhu, Q., Oganov, A. R., Glass, C. W., & Stokes, H. T. (2012). Constrained evolutionary algorithm for structure prediction of molecular crystals: methodology and applications. Acta Crystallographica Section B: Structural Science, 68(3), 215226. 6. Sankar, G. U., Moorthy, C. G., & RajKumar, G. (2018). Synthesizing graphene from waste mosquito repellent graphite rod by using electrochemical exfoliation for Battery/Supercapacitor Applications. Energy Sources, Part A: Recovery,

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International Journal of Advance Engineering and Research Development. 5. DOI: 10.21090/IJAERD.ICMNRE27. 8. Mahalingam, Vallikkodi & Sudhahar, S. (2018). Synthesis, Growth and characterization of Piperazinium salicylate Nonlinear

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10.13140/RG.2.2.20605.67046. 9. Mahalingam, Vallikkodi. (2018). Synthesis, growth and characterization of piperazinium p-aminobenzoate and piperazinium p-chlorobenzoate nonlinear optical single

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crystals. DOI: 10.13140/RG.2.2.16046.82243.

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