Nonlinear optical properties of thiazolidinone derivatives

Nonlinear optical properties of thiazolidinone derivatives

Available online at www.sciencedirect.com Optical Materials 31 (2009) 554–557 www.elsevier.com/locate/optmat Nonlinear optical properties of thiazol...

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Available online at www.sciencedirect.com

Optical Materials 31 (2009) 554–557 www.elsevier.com/locate/optmat

Nonlinear optical properties of thiazolidinone derivatives V. Smokal a,*, B. Derkowska b, R. Czaplicki c, O. Krupka a,c, A. Kolendo a, B. Sahraoui c a

Kyiv Taras Shevchenko National University, Volodymyrska 60, 01033 Kiev, Ukraine Institute of Physics, N. Copernicus University, Grudzia˛dzka 5/7, 87-100 Torun, Poland c Laboratory POMA, UMR CNRS 6136, University of Angers, 2 Bd. Lavoisier, 49045 Angers, France b

Received 15 July 2007; accepted 5 October 2007 Available online 5 February 2008

Abstract Thiazolidinone derivatives were synthesized and their physicochemical properties are determined by absorption, H NMR spectroscopies. The third order nonlinear optical properties of thiazolidinone containing compounds were investigated in solutions using degenerate four wave mixing (DFWM) method at 532 nm. Ó 2007 Elsevier B.V. All rights reserved. PACS: 42.65.Ky; 62.65.Wi Keywords: Methacrylic monomers; Nonlinear optical polymers; DFWM

1. Introduction

2. Experimental

The development of modern technologies enables us to create polymer materials with a number of properties, which would be impossible to realize in a single polymer [1–3]. Polymers represent a large family of materials, which have been studied for nonlinear optics. Thiazolidinone containing monomers have been the object of investigations because of their potential applications in the field of photonics and optoelectronics. Polymers based on them are very promising for reversible optical data storage, photo switching of optical elements, the orientation of photochromic polymers and all-optical processing. Finally, we have synthesized the new methacrylic monomers, the polymers containing the model fragment and investigated their spectral characteristics. The third order nonlinear optical properties of thiazolidinone containing compounds were investigated in solutions using degenerate four wave mixing (DFWM) method at 532 nm (see Fig. 1).

2.1. Materials

*

Corresponding author. Tel.: +380 442393300; fax: +380 442393100. E-mail address: [email protected] (V. Smokal).

0925-3467/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.optmat.2007.10.019

N,N-dimethylformamide (DMF) were vacuum-distilled off from calcium hydride just prior to use. 2,2’Azobis(isobutyronitrile) (AIBN) was recrystallized twice from absolute methanol. Methacrylic anhydride and methacryloyl chloride were vacuum-distilled, immediately before use. Methylmethacrylate (MMA) was dried by distillation under argon. All other reagents and solvents were commercially available and used as received.

2.2. Synthesis 2.2.1. (4-Hydroxyphenyl)methylene-2-thioxo-4thiazolidinone (p-I) 0.91 g of 4-hydroxybenzaldehyde were added to a solution of 2-thioxo-4-thiazolidinone 1 g, in isopropyl alcohol. The reaction mixture was heated for 2 h on a steam bath at 80–90 °C and then poured into water. The resultant solid product was collected, washed with cold ethanol, hot water, ethanol and then small amount of hexane and then

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R1O

O NH S S

R1= H (I), CH3CO (II), CH2C(CH3)CO (III), -C(CH3)-CH2- (IV) n CO Fig. 1. Chemical structures of thiazolidinone derivatives.

dried to afford compound p-I as yellow solid m.p. 283– 285 °C, yield 80%. 1H NMR (400 MHz, DMSO-d6), % (ppm): 7.49 (s, 1H, –CH@), 10.26 (s, 1H, –OH), 13.52 (s, 1H, –NH), 6.87–7.70 (m, 4H, Ph-H). UV–vis (ethanol) kmax: 242, 292, 395 nm. 2.2.2. (3-Hydroxyphenyl)methylene-2-thioxo-4thiazolidinone (m-I) This was obtained as described for p-I, m.p. 250–252 °C, yield 75%. 1H NMR (400 MHz, DMSO-d6), % (ppm): 7.47 (s, 1H, –CH@), 13.73 (s, 1H, –NH), 9.68 (s, 1H, –OH), 6.85–7.27 (m, 4H, Ph-H). UV–vis (ethanol) kmax: 252, 276, 380 nm. 2.2.3. (4-Acetyloxyphenyl)methylene-2-thioxo-4thiazolidinone (p-II) One gram (p-I) in acetic anhydride 3 ml was heated on a steam bath at 80–90 °C. After 2 h, the mixture was cooled and then poured into water. The resultant solid product that formed was filtered off, washed with water and dried. Crystallization from ethanol alcohol gave yellow crystals m.p. 238–240 °C, yield 70%. 1H NMR (400 MHz, DMSO-d6), % (ppm): 7.61 (s, 1H, –CH@), 2.29 (s, 3H, CH3), 13.75 (s, 1H, –NH), 7.25–7.50 (m, 4H, Ph-H). UV– vis (ethanol) kmax: 240, 266, 377 nm. 2.2.4. (3-Acetyloxyphenyl)methylene-2-thioxo-4thiazolidinone (m-II) This was obtained as described for (p-II), m.p. 175– 177 °C, yield 60%. 1H NMR (400 MHz, DMSO-d6), % (ppm): 7.58 (s, 1H, –CH@), 2.30 (s, 3H, –CH3), 13.73 (s, 1H, –NH), 7.22–7.53 (m, 4H, Ph-H). UV–vis (ethanol) kmax: 239, 264, 374 nm. 2.2.5. 4-(Methacryloyloxy)benzaldehyde A solution containing 4.9 g of 4-hydroxybenzaldehyde and 11.4 ml of triethylamine in 150 ml of diethyl ether was cooled to 0 °C. To the solution 8.4 g of methacryloyl chloride in 8 ml of diethyl ether was added dropwise in 40 min while stirring. The precipitated triethylammonium chloride was filtered off and the filtrate was allowed to stand for 12 h at 4 °C. The suspended matter formed in the solution was separated by filtration. Then the solvent

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was evaporated and the residue was dried to give 7.0 g (90%) of a pale yellow solid. 3-(methacryloyloxy)benzaldehyde was obtained analogously to 4-(methacryloyloxy)benzaldehyde. 2.2.6. 4-(Methacryloyloxyphenyl)methylene-2-thioxo-4thiazolidinone (p-III) A solution containing 2 g of 4-(methacryloyloxy)benzaldehyde, 2.5 g of 2-thioxo-4-thiazolidinone and 0.3 g of anhydrous sodium acetate in 50 ml isopraponol was heated on a steam bath at 80–90 °C. After 2 h, the mixture was cooled and then was poured on ice. The resultant solid product that formed was filtered off, washed with water and dried. Crystallization from ethanol alcohol gave yellow crystals m.p. 195 °C, 65%. 1H NMR (400 MHz, DMSOd6), % (ppm): 5.86 (s, 1H, CH2@), 6.31 (s, 1H, CH2@), 2.04 (s, 3H, –CH3), 7.28–7.66 (m, 4H, Ph-H), 7.62 (s, 1H, –CH@), 13.69 (s, 1H, –NH). 2.2.7. 3-(Methacryloyloxyphenyl)methylene-2-thioxo-4thiazolidinone (m-III) This was obtained as described for (p-III), m.p. 155 °C, yield 60%. 1H NMR (400 MHz, DMSO-d6), % (ppm): 5.87 (s, 1 H, CH2@), 6.33 (s, 1H, CH2@), 2.06 (s, 3H, –CH3), 7.29–7.54 (m, 4H, Ph-H), 7.60 (s, 1H, –CH@), 13.75 (s, 1H, –NH). The polymerization ability of the new monomers was investigated kinetically for radical homopolymerization using the dilatometric method. The process was conducted in 10% DMF solution at 80 °C (argon atmosphere, initiator – AIBN 1%); contractions were measured by KM-6 cathetometer. Monomers conversion during the homopolymerization process of (m-III) was 63% in 240 min with homopolymer (m-IV); for (p-III), the conversion was 67% in 261 min with homopolymer (p-IV), respectively. 2.3. Spectral measurements 1

H NMR (400 MHz) spectra were recorded on a ‘‘Mercury-400” spectrometer using DMSO-d6 as solvent. Chemical shifts are in ppm from the internal standard tetramethylsilane (TMS). UV–vis measurements in the 210–600 nm spectral region were performed at room temperature in ethanol in quartz cell (C = 105 mol/L) with a Perkin–Elmer UV/vis/NIR Lambda 19 spectrometer. The absorption spectra of compound p-II recorded during UV irradiation clearly indicate that this compound undergoes the photoisomerization process (Fig. 2). The observable results are typical of the cis– trans isomerization process for compounds with benzylidene fragment [4,5]. The stable state of the molecule with benzylidene fragment is the cis-isomeric configuration [6]. The absorption in the visible range of a photon induces the transition to the trans-isomer. This state is metastable with the reverse transition to the cis-state taking place through photo activation. Therefore, a molecule absorbing of a photon under-

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V. Smokal et al. / Optical Materials 31 (2009) 554–557

1

0.5

2

-5

2.0x10

Absorption

2

Intensity of I4 [ GW/cm ]

0.6

0.4 0.3 0.2 0.1

-5

1.6x10

p-II p-IV m-II m-IV

-5

1.2x10

-6

8.0x10

-6

4.0x10

0.0 250

300

350

400

450

500

0.0 0.0

Wavelength [nm] Fig. 2. Changes of the absorption spectrum p-II in ethanol (C = 105 mol/L) before (1) and after (2) 60 min of UV irradiation.

goes a complete cis–trans–cis isomerization cycle [7]. From the trans form, molecules come back to the cis form by two mechanisms – spontaneous thermal reactions and trans–cis photoisomerization. 2.4. DFWM experiment We used the standard backward degenerate four wave mixing (DFWM) method in order to quantify the refractive nonlinearities [8–10]. In this experiment, two beams interfere inside the sample to form a grating from which the third beam diffracts to form a phase-conjugate signal that retraces the probe path. The vh3i measurements were performed at room temperature and carried out with polarization directions of all three interacted laser beams aligned vertically (xxx). We used Nd:YAG laser working at 532 nm (30 ps, 1 Hz). Carbon disulfide (CS2) was used as reference to calibrate the DFWM measurement. All materials were contained in a 1 mm thick quartz cuvette. 3. Results and discussion The experimental and theoretical results of DFWM reflectivity (R) of studied compounds are presented in Fig. 3. In DFWM measurement, two pump beams (h1i and h2i) were counter propagating with the remaining 6% going to the probe beam (h3i). The probe beam was a small nonzero angle h (h = 12°) with respect to the pump beams. The three beams of the same frequency (x) were temporally and spatially overlapped in the sample. A phase-conjugated signal generated from the three laser beams (designated by h4i) was collected at a reverse direction of the probe beam. The vh3i measurements were carried out with polarization directions of all three interacted laser beams aligned vertically (xxx). The incident wave intensities verify the relations: I1(z = 0) = I2(z = L) and I3 = 6  102I1 (it means that 94% of the laser power was evenly split between the two counter propagating pumps pulse with the remaining 6% going to the probe pulse) [8–10]:

0.2

0.4 0.6 0.8 2 Intensity of I1 [ GW/cm ]

1.0

Fig. 3. DFWM reflectivity (R) of studied compounds as a function of the intensity of the incident beam I1. Table 1 The values of a and vh3i of studied compounds dissolved in DMF (C = 2.4 g/L) Compounds

a (cm1)

vh3i (esu)

CS2 DMF m-IV p-IV m-II p-II

0 0 2.11 2.23 2.48 2.61

1.26  1012 1.28  1012 1.28  1013 2.16  1013 1.92  1013 2.24  1013

I 4 ð0Þ I 4 ð0Þ ¼ I 3 ð0Þ 6  102 I 1 ð0Þ  2 48p3 h3i I 1 ð0ÞI 2 ð0Þ expðaLÞ v ; ¼ 2 n2 ck ½p cot hðpLÞ þ a2   2 2 3 h3i v I 1 ð0ÞI 2 ð0Þ and a, L, k, and n are where p2 ¼ a4  48p n2 ck the linear absorption coefficient, the thickness of the sample, the wavelength of the used laser and the linear refractive index of the considered material, respectively. The values of vh3i estimated from the quadratic dependencies of experimental data and formula are presented in Table 1. In order to determine the role of m- or p- substitute on NLO effect we used acetyl derivatives as modeling compounds of methacrilic monomers. We can see that the vh3i values of the para thiazolidinone derivatives p-II and p-IV are larger than the m- substituted compounds m-II and m-IV. We supposed that this behaviour comes from different photoisomerization processes of investigated compounds. The NLO effect of polymer is lower than the corresponding modeling compounds of methacrilic monomers due to steric factor. R¼

4. Conclusions New modeling compounds and their polymers were synthesized, characterized and their NLO properties were studied. Polymerization activities of new monomers were

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investigated dilatometrically. Their thermoinitiated polymerizations with methacrylic monomers were studied. These products were characterized by spectroscopic measurements. Extensive studies of new thiazolidone derivatives have shown favorable photophysical and photochemical properties, which has application in nonlinear optical materials. Acknowledgement This work is financially supported by the Ukrainian Ministry of Research 1 0101U002162. References [1] O. Krupka, A.Yu. Kolendo, K. Kushnir, J. Blazejowski, Mol. Cryst. Liq. Cryst. 427 (2005) 233.

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[2] V. Smokal, R. Czaplicki, B. Derkowska, O. Krupka, A. Kolendo, B. Sahraoui, Synthetic Met. 157 (2007) 708. [3] A. Fritz, A. Schonhals, B. Sapich, J. Stumpe, Macromol. Chem. Phys. 200 (1999) 2213. [4] E. F Ullman, N. Baumann, J. Am. Chem. Soc. 192 (1970) 5892. [5] K. Brocklehurst, K. Williamson, Tetrahedron 30 (1974) 351. [6] N. Baumann, E.F. Ullman, J. Am. Chem. Soc. 90 (1968) 4158. [7] Y.S. Rao, J. Org. Chem. 41 (1976) 722. [8] B. Sahraoui, G. Rivoire, Opt. Commun. 138 (1997) 109. [9] B. Derkowska, M. Wojdyla, W. Bala, K. Jaworowicz, M. Karpierz, J.G. Grote, O. Krupka, F. Kajzar, B. Sahraoui, J. Appl. Phys. 101 (2007) 083112. [10] B. Derkowska, J.C. Mulatier, I. Fuks, B. Sahraoui, X. Nguyen Phu, C. Andraud, J. Opt. Soc. Am. B – Opt. Phys. 18 (2001) 610.