Synthesis and properties of 1,3-dioxo-1 H - inden-2(3 H )-ylidene - PowerPoint PPT Presentation

Synthesis and properties of 1,3-dioxo-1 H - inden-2(3 H )-ylidene fragment and (3- (dicyanomethylene)-5,5-dimethylcyclohex-1- enyl)vinyl fragment containing derivatives of azobenzene for holographic recording materials Elm ā rs Zari ņ š, Valdis Kokars, Andris Ozols, P ē teris Augustovs P ē teris Augustovs Riga Technical University, LATVIA SPIE OPTICS + OPTOELECTRONICS 2011 Holography: Advances and Modern Trends

Photoisomerization of azobenzene and Surface Relief Grating (SRG) formation: * Ostroverkhova, O. and Moerner, W. E., "Organic Photorefractives: Mechanisms, Materials, and Applications", Chem. Rev. 104, 3267-3314 (2004); ** Yager, K.G. and Barrett, C.J., "Light-Induced Nanostructure Formation using Azobenzene Polymers ", Polymeric Nanostructures and Their Applications 0, 1–38 (2006).

1. Synthesis of azo group containing aldehydes 3a-b : O H CH 3 C Na 2 S . 9H 2 O, S, NaOH EtOH 64% NO 2 NH 2 1 2 R 2 R O N N 1. NaNO 2 , HCl/H 2 O N 2 R 2 H O H H N O 3a, 3b 2. 3a) R 2 = Et- 3b) R 2 = -CH 2 CH 2 OH 79-83% * Campaigne, E., Budde, W.M. and Schaefer. G.F., "p-Aminobenzaldehyde", Org. Synth. Coll. 4, 31 (1963) and 6, 31 (1951). ** Woo, H.Y., Shim, H.-K. and Lee, K.-S. "Synthesis and optical properties of polyurethanes containing a highly NLO active chromophore", Marcomol. Chem. Phys. 199, 1427-1422 (1998).

2. Synthesis of 1,3-dioxo-1 H -inden-2(3 H )-ylidene fragment containing amorphous azobenzene derivatives O H O R 2 O Piperidine O N N N N Et-OH N O R 2 N 59-69% H O H 3a, 3b O 5a) R 2 = Et- 5a, 5b 4 5b) R 2 = -CH 2 CH 2 OH l C - C C h 3 h 3 Py, Et 3 N t N Ph 3 Si-Cl Ph 3 Si-Cl P P Py, Et 3 N 73-90% 41% Ph Ph O Ph O Si Ph O O Ph Ph N N N N O R 3 N O N 6a, 6b 7 O 6a) R 3 = Et- Ph Si 6b) R 3 = -CH 2 CH 2 OC(Ph) 3 Ph Ph

3. Synthesis of (3-(dicyanomethylene)-5,5-dimethylcyclohex- 1-enyl)vinyl fragment containing amorphous azobenzene derivative 12: O H O N N N H O H 3b

4. Sample preperation: The obtained compounds 6a , 6b , 7 and 12 were spin-coated on glass substrate from their saturated solutions of chloroform: Ph O Ph O Ph N N N N O R 3 N 6a, 6b 6a) R 3 = Et- 6b) R 3 = -CH 2 CH 2 OC(Ph) 3 Ph O Si Ph O Ph N N O N * http://www.semiconductor.net/photo/173/173195-02svg4a.gif 7 O Ph Si Ph Ph

5. Holographic recording setup with p-p polarizations of recording beams: Photodiode PD detects SDE Photodiode PD A detects SDE t Photodiode PD B detects SDE r Laser 1: Melles Griot 25LH928-230 He-Ne gas laser (recording and readout wavelengths λ 1 = λ 2 = 632.8 ~ 633 nm) Laser 2: KLASTECH DENICAFC 532-300 diode pumped solid state laser (recording and readout wavelengths λ 1 = λ 2 = 532 nm) * Ozols, A., Kokars, V., Augustovs, P., Uiska, I., Traskovskis, K., Mezinskis, G., Pludons, A. and Saharov. D., "Polarization dependence of holographic recording in glassy azocompounds", Lith. J. Phys. 50, 17-2 5 (2010).

6. Holographic data storage parameters SDE is a ratio of a first-order diffracted beam power to the power of the more distant recording beam without the interruption of recording beams. W max = It max /SDE max ; W max - Specific Recording Energy W max - Specific Recording Energy REF max = SDE max /W max [(cm %) 2 /J] ; REF max -Recording Efficiency Factor * Ozols, A., Kokars, V., Augustovs, P., Uiska, I., Traskovskis, K., Mezinskis, G., Pludons, A. and Saharov. D., "Polarization dependence of holographic recording in glassy azocompounds", Lith. J. Phys. 50, 17-2 5 (2010).

7. Amorphous film holographic data storage parameters at 632.8 nm: Sample I, SDE t W t , REF t , SDE r , W r , REF r , W/cm 2 , kJ/cm 2 (%cm) % kJ/cm 2 % (%cm) % % 2 /kJ 2 /kJ 6a 1.42 2.98 0.69 4.3 3.02 0.67 4.4 6b 1.41 1.50 1.35 1.11 1.13 1.80 0.62 7 1.41 1.08 1.73 1.7 0.875 2.32 0.38 1.42 9.9 0.21 48 2.1 0.99 2.1 12 Ph Ph O Si Ph O Ph O O Ph Ph N N N N O O R 3 N N 6a, 6b 7 O Ph 6a) R 3 = Et- Si 6b) R 3 = -CH 2 CH 2 OC(Ph) 3 Ph Ph

8. Amorphous film holographic data storage parameters at 532 nm: Sample I, SDE t , W t , REF t , SDE W r , REF r , W/cm 2 % kJ/cm 2 % (%cm) 2 /kJ r , % kJ/cm 2 (%cm) 2 /kJ % 6a 1.19 0.58 2.9 0.20 3.1 0.30 10.4 13.6 0.79 17 0.99 8.6 0.115 6b 1.34 0.022 88 0.25 0.71 2.7 0.26 7 1.35 0.37 5.3 0.069 0.81 0.40 2.0 12 1.28 15.3 0.113 135 2.45 63 0.039 Ph Ph O Si Ph O Ph O O Ph Ph N N N N O O R 3 N N 6a, 6b 7 O Ph 6a) R 3 = Et- Si 6b) R 3 = -CH 2 CH 2 OC(Ph) 3 Ph Ph

Conclusions: All synthesized compounds ( 6a , 6b , 7 and 12 ) are characterized � with intensive absorption in UV-VIS spectrum red light region (440-640nm). They also form thin solid amorphous films from volatile organic solvents (dicholomethane and chloroform). That makes them perspective with their potential application in obtaining and researching holographic materials with 532 nm and obtaining and researching holographic materials with 532 nm and 633 nm lasers. Experimentally studying holographic properties of these � compounds at 633 and 532 nm in transmission and reflection modes, isophorene fragment containing film 12 was found to be the most efficient at both wavelengths in transmission mode exhibiting the maximum self-diffraction efficiency of 9.9% at 633 nm, and 15.3% at 532 nm. The mono trityloxiethylamino film 6a was the most efficient in reflection mode with the maximum self- diffraction efficiency of about 3%.

ACKNOWLEDGEMENTS This work has been supported by the European Social Fund within the project «Support for the implementation of doctoral studies at Riga Technical University».

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