• Bulletin of the Korean Chemical Society
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• v.33 no.6
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• pp.1900-1906
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• 2012

Three carbazole chromophores featuring dicyano, cyano, ethyl acetate and dimethyl acetate groups as an acceptor moiety with a ${\pi}$-conjugated spacer and $N$-methyl dibenzo[$b$]pyrole as donor were synthesized by Knovenagel condensation and characterized by IR, $^1HNMR$, $^{13}CNMR$, UV-vis, fluorescence spectroscopy, electrochemistry and theoretical B3LYP/6-$311G^*$ level whilst NLO properties and spectroscopic quantities were calculated. Calculations showed remarkable trend with HOMO located on the donor moiety and LUMO on the acceptors dicyano methylene, cyano, ethyl acetate methylene and dimethyl acetate methylene. In agreement with the calculations, solvatochromic, behavior intramolecular charge transfer band was observed in the visible region.

• Bulletin of the Korean Chemical Society
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• v.19 no.2
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• pp.155-159
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• 1998

o-(2-Vinyloxyethoxy)benzylidenemalononitrile (4a), methyl o-(2-vinyloxyethoxy)benzylidenecyanoacetate (4b), m-(2-vinyloxyethoxy)benzylidenemalononitrile (5a), methyl m-(2-vinyloxyethoxy)benzylidenecyanoacetate (5b), p-(2-vinyloxyethoxy)benzylidenemalononitrile (6a), and methyl p-(2-vinyloxyethoxy)benzylidenecyanoacetate (6b) were prepared by the condensation of o-(2-vinyloxyethoxy)benzaldehyde (1), m-(2-vinyloxyethoxy)benzaldehyde (2), and p-(2-vinyloxyethoxy)benzaldehyde (3) with malononitrile or methyl cyanoacetate, respectively. Bifunctional vinyl ether monomers 4a-b and 6a-b polymerized readily with cationic initiators to give polymers with the NLO-chromophores o- and p-oxybenzylidenemalononitrile or o- and p-oxybenzylidenecyanoacetate in side chain at -60 ℃, while meta-isomers 5a and 5b gave lower yields of polymers under the same conditions. The resulting polymers 7-9 were soluble in common organic solvents and the inherent viscosities of polymers were in the range of 0.20-0.30 dL/g in acetone. Solution-cast films were clear and brittle, showing Tg values in the range of 40-70 ℃.

• Bulletin of the Korean Chemical Society
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• v.26 no.1
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• pp.77-84
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• 2005

We prepared the new nonlinear optical chromophores that show fairly high microscopic nonlinearity through intramolecular charge transfer. Phenothiazine and carbazole units played an important role to contribute high electron donability and connect the resonance pathway via conjugative effect in the cyclized ring beside the aromatic ring. Theoretical calculation, electrochemical analysis, and absorption spectroscopic study gave us useful information about the energy states and microscopic nonlinearities of two serial chromophores. We compared the microscopic nonlinearities of four chromophores with the conjugation length and electron donability in the push-pull type NLO chromophores. The effect of gradient donability and lengthening the conjugation were investigated on the electronic state and microscopic nonlinearity.

• Macromolecular Research
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• v.14 no.6
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• pp.603-609
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• 2006

Tricyanopyrrolidene chromophores were prepared in order to compare their macroscopic nonlinear optical (NLO) properties with a conjugated structure through the long molecular axis. A thiophene or phenyl ring was tethered to an ethylenic bond; it may act as a lateral moiety to disrupt the planarity of a chromophore and lessen the electrostatic interaction. Thin film composites of these chromophores dissolved in amorphous polycarbonate (APC) were fabricated. Real time pole and probe method was employed to investigate the change of electro-optic (EO) signal during poling. The EO properties and their relaxation behaviors of the guest-host systems containing newly synthesized chromophores were investigated in detail.

• Macromolecular Research
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• v.17 no.11
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• pp.874-878
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• 2009

Photorefractive polymer composites were synthesized based on poly (N-vinylcazbazole) (PVK) doped with liquid nonlinear optical chromophores and a sensitizer $C_{60}$. PVK/liquid NLO chromophores/$C_{60}$ devices showed no signs of phase separation and did not require a plasticizer, such as ethylcarbazole. The composites showed 69% diffraction efficiency (C3) and a rapid response time of 46 ms (C1) in four-wave mixing experiments at a light intensity of $60\;mW/cm^2$ and a wavelength of 633 nm.

• Bulletin of the Korean Chemical Society
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• v.29 no.1
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• pp.181-186
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• 2008

2,5-Di-(2'-hydroxyethoxy)-4'-nitrostilbene (3) was prepared and polycondensed with terephthaloyl chloride, adipoyl chloride, and sebacoyl chloride to yield novel T-type polyesters (4-6) containing the NLO-chromophores dioxynitrostilbenyl groups, which constituted parts of the polymer backbones. Polymers 4-6 are soluble in common organic solvents such as acetone and N,N-dimethylformamide. They showed thermal stability up to 260 oC in thermogravimetric analysis with glass-transition temperatures obtained from differential scanning calorimetry in the range 90-95 oC. The second harmonic generation (SHG) coefficients (d33) of poled polymer films at the 1064 nm fundamental wavelength were around 1.42 ´ 10-9 esu. The dipole alignment exhibited high thermal stability up to 5 oC higher than glass-transition temperature (Tg), and there was no SHG decay below 100 oC due to the partial main-chain character of polymer structure, which is acceptable for NLO device applications.

• Macromolecular Research
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• v.12 no.5
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• pp.484-489
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• 2004

We have prepared a phenothiazine-based nonlinear optical (NLO) chromophore that displays a fairly high microscopic nonlinearity through intramolecular charge transfer. The phenothiazine unit plays important roles of contributing its high electron donating ability and connecting the resonance pathway through a conjugative effect in the cyclized ring adjacent to the aromatic ring. Theoretical calculations and an absorption spectroscopic study provided useful information concerning the microscopic nonlinearity of the chromophores. We investigated the electro-optic (EO) properties of the guest-host systems in amorphous polycarbonate containing the synthesized chromophores at different concentrations under different poling temperatures. A real-time pole and probe method provided a much greater amount of information regarding how the EO properties can arise and how they can be optimized.

• 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.

• Macromolecular Research
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• v.15 no.1
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• pp.59-64
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• 2007

Star-shaped, nonlinear optical (NLO) material was synthesized and its optical, thermal, and electro-optic properties were investigated. Three NLO-active dipolar chromophores containing a phenylene ring substituted with a bulky alkyl chain as a conjugation bridge were chemically bonded to the core of 1,1,1-tris(4-hydroxyphenyl)ethane to form a dendritic architecture. The chemical structure and purity of the chromophore were verified by NMR spectroscopy. The chromophore exhibited a broad absorption band centered at around 608 nm tailing up to 760 nm in toluene solution and also showed a discernible solvatochromic shift in more polar solvent. The chloroform solution of the dendrimer produced an absorption band with a red-shifted maximum as large as 28 nm when compared to that of the toluene solution. It was thermally stable up to $275^{\circ}C$ in a nitrogen atmosphere and had a glass transition temperature of $76^{\circ}C$. In a preliminary result, the polymer film containing the dendritic compound exhibited a shift of 19 pm/V taken at $1.55{\mu}$.

• Bulletin of the Korean Chemical Society
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• v.32 no.9
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• pp.3361-3366
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• 2011

New Y-type polyester (3) containing nitrophenylazoresorcinoxy groups as NLO chromophores, which are components of the polymer backbone, was prepared and characterized. Polyester 3 is soluble in common organic solvents such as N,N-dimethylformamide and acetone. It shows a thermal stability up to $240^{\circ}C$ in thermogravimetric analysis with glass-transition temperature ($T_g$) obtained from differential scanning calorimetry near $116^{\circ}C$. The second harmonic generation (SHG) coefficient ($d_{33}$) of poled polymer film at the 1064 nm fundamental wavelength is around $4.63{\times}10^{-9}$ esu. The dipole alignment exhibits a thermal stability even at $4^{\circ}C$ higher than $T_g$, and there is no SHG decay below $120^{\circ}C$ due to the partial main-chain character of polymer structure, which is acceptable for NLO device applications.