• Journal of Photoscience
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• v.10 no.2
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• pp.203-208
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• 2003

Two coupled molecules were successfully synthesized by condensation of amine-donor-substituted barbituric acid derivativies as nonlinear optical chromophores. A flexible spacer of the alkyl chain with different lengths of carbon chains (5 and 6 carbons) was introduced between two chromophores, which prevented crystallization and aggregation of molecules. Two coupled molecules (B-Cn-B, n=5, 6) had glass-transition temperatures on a second heating around 81 and 76$^{\circ}C$ without melting points, respectively. To explore the linear optical properties, thin-films were prepared and examined by a photometry method using Nd:YVO$_4$ CW laser. Also, microscopic and macroscopic nonlinear optical properties were measured by Hyper-Rayleigh Scattering (HRS) and the Maker Fringes method using Nd:YAG ps pulse laser, respectively. In spite of the moderate hyperpolarizabilities of coupled molecules, the second order NLO coefficient (d$\_$33/) was larger than the conventional Disperse Red 1 doped PMMA polymeric system.

• Bulletin of the Korean Chemical Society
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• v.32 no.2
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• pp.673-680
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• 2011

The compound 3-(2-Mercaptopyridine)phthalonitrile has been synthesized and characterized by IR, UV-vis, and X-ray single-crystal determination. The molecular geometry from X-ray determination of the title compound in the ground state has been compared using the Hartree-Fock (HF) and density functional theory (DFT) with the 6-31G(d) basis set. The calculated results show that the DFT and HF can well reproduce the structure of the title compound. The energetic behavior of the title compound in solvent media was examined using the B3LYP method with the 6-31G(d) basis set by applying the Onsager and polarizable continuum model. Using the TD-DFT and TD-HF methods, electronic absorption spectra of the title compound have been predicted and good agreement with the TD-DFT method and the experimental determination was found. The predicted nonlinear optical properties of the title compound are much greater than those of urea. Besides, molecular electrostatic potential of the title compound were investigated by theoretical calculations. The thermodynamic properties of the compound at different temperatures have been calculated and corresponding relations between the properties and temperature have also been obtained.

• Bulletin of the Korean Chemical Society
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• v.32 no.2
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• pp.424-430
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• 2011

A novel T-type polyurethane 7 containing 1-(2,5-dioxyphenyl)-2-(5-(1,2,2-tricyanovinyl)-2-thienyl)ethenes as NLO chromophores, which constitute part of the polymer backbone, was prepared. Polyurethane 7 is soluble in common organic solvents such as DMF and DMSO. It shows a thermal stability up to $270^{\circ}C$ from TGA thermogram with $T_g$ value obtained from DSC thermogram near $155^{\circ}C$. The second harmonic generation (SHG) coefficient ($d_{33}$) of poled polymer film at 1560 nm fundamental wavelength is $3.56{\times}10^{-9}$ esu. Polymer 7 exhibits a thermal stability even at $5^{\circ}C$ higher than $T_g$, and no significant SHG decay is observed below $160^{\circ}C$, which is acceptable for nonlinear optical device applications.

• Journal of the Korean Crystal Growth and Crystal Technology
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• v.13 no.4
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• pp.153-156
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• 2003

Pure and Ethylenediaminetetraacetic acid (EDTA) doped L-arginine phosphate (LAP) single crystals were grown from the aqueous solution by temperature lowering method. The effect of EDTA additive on the solubility and metastable zone width of LAP solution has been investigated. Addition of EDTA has enhanced the metastable zone width of LAP and hence bulk crystals could be grown. The growth rate along the [100] direction increases with EDTA additive. Powder X-ray diffraction and FTIR studies reveal the absence of EDTA in the lattice of LAP, This reveals that the addition of EDTA to LAP doesn't influence the crystallinity. However, the transmittance and NLO properties significantly increase with EDTA additive and hence bulk LAP crystals are useful for laser fusion experiments.

• Bulletin of the Korean Chemical Society
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• v.31 no.2
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• pp.429-434
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• 2010

A novel T-type polyester 7 containing 1-(2,5-dioxyphenyl)-2-{5-(1,2,2-tricyanovinyl)-2-thienyl}ethenes as nonlinear optical (NLO) chromophores, which are part of the polymer backbone, was prepared and characterized. Polyester 7 is soluble in common organic solvents such as dimethylsulfoxide and N,N-dimethylformamide. It showed a thermal stability up to $300^{\circ}C$ in thermogravimetric analysis thermogram and the glass-transition temperature ($T_g$) obtained from differential scanning calorimetry thermogram was around $113^{\circ}C$. The second harmonic generation (SHG) coefficient ($d_{33}$) of poled polymer films at 1,560 nm fundamental wavelength was around 1.85 pm/V. The dipole alignment exhibits a greater thermal stability even at $10^{\circ}C$ higher than $T_g$, and there is no SHG decay below $125^{\circ}C$ due to the partial mainchain character of the polymer structure, which is acceptable for nonlinear optical device applications.

• Macromolecular Research
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• v.15 no.6
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• pp.506-512
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• 2007

2,3-Di-(2'-hydroxyethoxy)-4'-nitrostilbene (3) was prepared and condensed with terephthaloyl chloride, adipoyl chloride, and sebacoyl chloride to yield novel Y-type polyesters (4-6) containing the NLO-chromophores 2,3-dioxynitrostilbenyl groups, which constituted parts of the polymer backbones. Polymers 4-6 were soluble in common organic solvents such as acetone and N,N-dimethylformamide. Polymers 4-5 showed thermal stability up to $300^{\circ}C$ in thermogravimetric analysis with glass transition temperatures $(T_g)$, obtained from differential scanning calorimetry, in the range $81-95^{\circ}C$. The second harmonic generation (SHG) coefficients $(d_{33})$ of the poled polymer films at the 1064 nm fundamental wavelength were around $3.68{\times}10^{-9}$ esu. The dipole alignment exhibited high thermal stability up to $T_g$, and there was no SHG decay below $T_g$ due to the partial main-chain character of the polymer structure.

• Macromolecular Research
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• v.11 no.4
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• pp.250-255
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• 2003

We prepared the photorefractive sol-gel glass based on organic-inorganic hybrid materials containing a charge transporting molecule, second-order nonlinear optical (NLO) chromophore, photosensitizer, and plasticizer. Carbazole and 2-{ 4-[(2-hydroxy-ethyl)-methyl-amino]-benzylidene}-malononitrile were reacted with isocyanato-triethoxy silane and the functionalized silanes were employed to fabricate the efficient photorefractive media induding 2,4,7-trinitrot1uorenone (TNF) to form a charge transfer complex. The prepared sol-gel glass samples showed a large net gain coefficient and high diffraction efficiency at a certain composition. As the concentration of photosensitizer increased, the photorefractive properties were enhanced due to an increment of charge carrier density. Dynamic behavior of the diffraction efficiency was also investigated with the concentration of the photosensitizer.

• Bulletin of the Korean Chemical Society
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• v.29 no.4
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• pp.811-816
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• 2008

2,5-Di-(2'-hydroxyethoxy)benzylidenemalononitrile (3) was prepared and polymerized with 2,4-toluenediisocyanate and 3,3'-dimethoxy-4,4'-biphenylenediisocyanate to yield novel T-type polyurethanes 4 and 5 containing 2,5-dioxybenzylidenemalononitrile, nonlinear optical (NLO)-chromophores as part of the polymer backbones. Polyurethanes 4 and 5 were soluble in common organic solvents such as acetone and N,Ndimethylformamide and showed a thermal stability up to $250{^{\circ}C}$ with glass-transition temperatures ($T_g$) in the range $119-146{^{\circ}C}$. The second harmonic generation (SHG) coefficients ($d_{33}$) of poled polymer films at 1064 nm fundamental wavelength were around $5.82{\times}10^{-9}$ esu. The dipole alignment exhibited high thermal stability up to $T_g$, and there was no SHG decay below $140{^{\circ}C}$ due to the partial main-chain character of the polymer structure, which was acceptable for nonlinear optical device applications.

• Bulletin of the Korean Chemical Society
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• v.30 no.5
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• pp.1080-1084
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• 2009

Methyl 2,4-di-(2'-hydroxyethoxy)benzylidenecyanoacetate (3) was prepared and polymerized with terephthaloyl chloride to yield a novel Y-type polyester 4 containing 2,4-dioxybenzylidenecyanoacetate groups as NLOchromophores, which constituted parts of the polymer backbone. The resulting polymer 4 is soluble in common organic solvents such as acetone and N,N-dimethylformamide. Polymer 4 showed thermal stability up to 280 ${^{\circ}C}$ in thermogravimetric analysis with glass-transition temperature obtained from differential scanning calorimetry near 108 ${^{\circ}C}$. The second harmonic generation (SHG) coefficient ($d_{33}$) of poled polymer films at the 1064 nm fundamental wavelength was around $3.54\;{\time}\;10^{-9}$ esu. The dipole alignment exhibited a thermal stability up to near $T_g$ and no significant SHG decay was observed below 100 ${^{\circ}C}$ due to the partial main-chain character of polymer structure, which is acceptable for NLO device applications.

• Polymer(Korea)
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• v.24 no.6
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• pp.737-743
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• 2000

Polyquinonediimines (PQDI) which have stable structure on heat and contains mono-azobenzene in the side chain were synthesized by means of condensation polymerization under TiCl$_4$. The synthesized monomers and polymers were identified by FT-IR, $^1$H-NMR, and elementary analysis. Especially, PQDI was comfirmed by the double-bonding peak of >C=N appeared near 1625 $cm^{-1}$ / by means of FT-IR spectrum. PQDI containing mono-azobenzene group in both side chains wat not soluble in non-polar solvents at all but partially soluble in the polar solvents having small dielectric constant, and dissolved in the strong acid such as sulfuric acid and $CH_3$SO$_3$H. Molecular weight distribution of PQDI measured by GPC showed 1.74. It was confirmed through X-ray diffraction analysis that the polymer was partially crystalline at the low angle region, but amorphous after heat treatment at 1$25^{\circ}C$. The glass transition temperature (T$_{g}$ ) of synthesized polymer was measured as 1$25^{\circ}C$ by differential scanning calorimetry. The SHG value for $\chi$$^{(2)}$ after poling at 1$25^{\circ}C$ was 8.6 pm/V (λ=1.542 ${\mu}{\textrm}{m}$). The SHG value slowly decreased with time from the start but appeared temporal stability after 100 hours.