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

Synthesis and properties of 1,3-dioxo-1H- inden-2(3H)-ylidene fragment and (3- (dicyanomethylene)-5,5-dimethylcyclohex-1- enyl)vinyl fragment containing derivatives of azobenzene for holographic recording materials Elmārs Zariņš, Valdis Kokars, Andris Ozols, Pēteris Augustovs Pēteris 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 :

CH3 NO2 C NH2 O H Na2S.9H2O, S, NaOH EtOH 1 2 64% R2 * Campaigne, E., Budde, W.M. and Schaefer. G.F., "p-Aminobenzaldehyde", Org. Synth. Coll. 4, 31 (1963) and 6, 31 (1951). N N H O N R O H N R2 O H

• 1. NaNO2, HCl/H2O

3a) R2 = Et- 3b) R2 = -CH2CH2OH 3a, 3b 79-83% 2. 2

** 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).

N N H O N R2 O H 3a, 3b 5a) R2 = Et- 5b) R2 = -CH2CH2OH N N N R2 O H Et-OH O O O O 4 5a, 5b 59-69% Piperidine

t N P h3 C

• C

l

Ph3Si-Cl

• 2. Synthesis of 1,3-dioxo-1H-inden-2(3H)-ylidene fragment

containing amorphous azobenzene derivatives

73-90% Py, Et3N P h3 C

6a) R3 = Et- 6b) R3 = -CH2CH2OC(Ph)3 N N N R3 O O O Ph Ph Ph 6a, 6b Ph3Si-Cl Py, Et3N 41%

N N N O Si O O Ph Ph Ph 7 O Si Ph Ph Ph

• 3. Synthesis of (3-(dicyanomethylene)-5,5-dimethylcyclohex-

1-enyl)vinyl fragment containing amorphous azobenzene derivative 12:

N N H O N O H 3b O H

• 4. Sample preperation:

The obtained compounds 6a, 6b, 7 and 12 were spin-coated on glass substrate from their saturated solutions of chloroform:

N N O O Ph Ph Ph

* http://www.semiconductor.net/photo/173/173195-02svg4a.gif

6a) R3 = Et- 6b) R3 = -CH2CH2OC(Ph)3 N N N R3 O 6a, 6b

N N N O Si O O Ph Ph Ph 7 O Si Ph Ph Ph

• 5. Holographic recording setup with p-p polarizations of

recording beams:

Photodiode PD detects SDE Photodiode PDA detects SDEt Photodiode PDB detects SDEr * 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, 17-25 (2010). Laser 1: Melles Griot 25LH928-230 He-Ne gas laser (recording and readout wavelengths λ1 = λ2 = 632.8 ~ 633 nm) Laser 2: KLASTECH DENICAFC 532-300 diode pumped solid state laser (recording and readout wavelengths λ1 = λ2 = 532 nm)

• 6. Holographic data storage parameters

SDE is a ratio of a first-order diffracted beam power to the power

• f the more distant recording beam without the interruption of

recording beams. Wmax = Itmax /SDEmax ; Wmax - Specific Recording Energy Wmax - Specific Recording Energy

* 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, 17-25 (2010).

REFmax = SDEmax/Wmax [(cm %)2/J]; REFmax-Recording Efficiency Factor

• 7. Amorphous film holographic data storage parameters at 632.8

nm:

Sample I, W/cm2 SDEt , % Wt , kJ/cm2 % REFt , (%cm)

2/kJ

SDEr , % Wr , kJ/cm2% REFr, (%cm)

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 12 1.42 9.9 0.21 48 2.1 0.99 2.1

6a) R3 = Et- 6b) R3 = -CH2CH2OC(Ph)3 N N N R3 O O O Ph Ph Ph 6a, 6b

N N N O Si O O Ph Ph Ph 7 O Si Ph Ph Ph

• 8. Amorphous film holographic data storage parameters at 532

nm:

Sample I, W/cm2 SDEt, % Wt , kJ/cm2% REFt , (%cm) 2/kJ SDE

r , %

Wr , kJ/cm2 % REFr, (%cm) 2/kJ 6a 1.19 0.58 13.6 2.9 0.79 0.20 17 3.1 0.99 0.30 8.6 10.4 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

6a) R3 = Et- 6b) R3 = -CH2CH2OC(Ph)3 N N N R3 O O O Ph Ph Ph 6a, 6b

N N N O Si O O Ph Ph Ph 7 O Si Ph 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

• btaining and researching holographic materials with 532 nm and
• btaining and researching holographic materials with 532 nm and

633 nm lasers.

• Experimentally

studying holographic properties

• f

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».

Thank you for your attention!!!