• Title/Summary/Keyword: charge transfer complex

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Optical Transmittance of Polybenzoxazole Precursor (폴리벤조옥사졸 전구체의 광투과도 연구)

  • 김대겸;김종화;최길영;오재민;이무영;박동원;이광섭;진문영
    • Polymer(Korea)
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    • v.26 no.1
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    • pp.18-27
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    • 2002
  • Poly(ο-hydroxyamide)s as polybenzoxazoles precursors were synthesized by polycondensation from 2,2'-bis(3-amino-4-hydroxyphenyl) hexafluoropropane and various bis-acids. And the polymers were modified to acid-sensitive polyamides by introducing tetrahydropyran in order to impart photosensitivity. A study of optical transmittance at 365 nm, according to the chemical structure of bis-acid, revealed that the polymer derived from 4,4'-oxydibenzoic acid showed better optical transparency than those from other bis-acids. This tendency of optical transmittance could be explained by formation of charge transfer complex. In case of the polymer derived from 4,4'-oxydibenzoic acid, the electron accepting characteristic of bis-acid is reduced by introduction of electron donating group, -O-. Thus, optical transmittance increased due to the diminished formation of intramolecular charge transfer complex. In addition, the optical transmittance increased with increasing the THP content in the polymer. This is attributed to the reduced intermolecular interaction by the loosening of the packing density of the polymer chain.

The Effects of Charge Transfer Complex on the Reaction of Aniline and Iodine (Aniline과 Iodine간의 반응에 있어서 전하이동 착물의 영향)

  • Oh-Yun Kwon;U-Hyon Paek;Eung-Ryul Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.174-179
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    • 1992
  • Reaction of aniline and iodine in$CHCl_3,\;CH_2Cl_2 : CHCl_3$(1 : 1), and $CH_2Cl_2$ has been studied kinetically by using conductivity method, Pseudo first-order rate constants ($k_{obs}$) and second-order rate constants ($k_{obs}$/[aniline]) are dependent on the aniline concentration. Second-order rate constants obtained were increased with increasing aniline concentration. We analysed these results on the basis of formation of charge transfer complex as reaction intermediate. From the construction of react ion scheme and derivation of rate equation, we calculated equilibrium constants and activation parameters for the formation and transformation of charge transfer complex. The equilibrium constants were decreased by an increase in the dielectric constant of the solvent and the value is 1.7-3.7$M^{-1}$. The rate of transformation are markedly affected by the solvent polarity. ${\Delta}H^{\neq}$ is about 14.2kJ/mol, and ${\Delta}S^{\neq}$ is large negative value of -243J/mol K.

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Effects of Polyelectrolytes on the Charge Transfer Complexing between Indole derivatives and Methylviologen: Hydrophobic and Electrostatic Interactions

  • Park, Joon-Woo;Hwang, Book-Kee
    • Bulletin of the Korean Chemical Society
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    • v.6 no.3
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    • pp.145-148
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    • 1985
  • The effect of anionic polyelectrolytes, poly(styrenesulfonate) (PSS) and poly(vinylsulfonate) (PVS), on the charge transfer complexing between indole derivatives and methyl viologen($MV^{++}$) cation was investigated. The results were compared with effect of NaCl and an anionic surfactant, sodium dodecylsulfate (SDS). Both PSS and PVS enhanced the complex formation of neutral species (indole and indole acetate at low pH), zwitter ionic tryptophan, and positively charged tryptamine and tryptophan at low pH with $MV^{++}$. This result was attributed to the contribution of hydrophobic interaction, in addition to electrostatic interaction. The enhancing effect of PSS was much higher than that of PVS reflecting the higher hydrophobicity of PSS. The interaction between indole acetate anion and $MV^{++}$ was greatly reduced by addition of PVS and PSS. The higher charge density of PVS was appeared as greater reducing effect indicating the importance of electrostatic force in this case. In all cases, the effect of polyelectrolytes showed maxima, and further addition of PVS and PSS decreased the effect. This behavior was explained in terms of distribution of indole derivatives and $MV^{++}$ in domain of polyanions. The complex formation constants and molar absorptivities of complexes were determined, and the values were compared with those in water and SDS solutions.

Silsesquioxane/Polystyrene Hybrid Materials via Charge Transfer Interactions (전하 이동을 이용한 실세스퀴옥산/폴리스티렌 하이브리드)

  • Choi, Ji-Won;Chujo, Yoshiki
    • Polymer(Korea)
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    • v.31 no.2
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    • pp.136-140
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    • 2007
  • Charge transfer interaction as a hybridization mechanism of silsesquioxane/polymer was tested using carbazole (electron donor) group and dinitrobenzene (electron acceptor) group. Hybridization test was conducted using films made from mixing/casting of poly (carbazole-styrene) (PS/D) and dimtrobenzyl silsesquioxane (Cube/A), and transparent hybrid films were successfully obtained under some conditions. $^1H-NMR$ of PS/D and Cube/A, and W absorption test of hybrid films showed that one acceptor and one donor can form one charge transfer complex when no silsesquioxane molecule was included in films, but transparent hybrids with no phase separation were obtained only at acceptor/donor ratios less than 0.7 : 1. These results also suggested that on average 4 charge transfer complexes form per one silsesquioxane.

Charge-Transfer Complex Formation between Stilbenes and 7,7,8,8-Tetracyanoquinodimethane

  • Jin, Jung-Il;Kim, Joon-Seop;Kim, Jeong-Deuk
    • Bulletin of the Korean Chemical Society
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    • v.9 no.3
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    • pp.167-171
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    • 1988
  • Formation of intermolecular charge-transfer complexes between 7,7,8,8-tetracyanoquinodimethane (TCNQ) and two different series of stilbene derivatives has been studied spectroscopically at $25^{\circ}$C in 1,2-dichloroethane. The compounds of Series I include stilbene and derivatives which have fused phenyl rings on one end of the central ethylene structure and a phenyl ring on the other end. The other Series, II, is comprised of stilbenes which have various para substituents on one of the two phenyl rings. The equilibrium constant, $K_c^{AD}$ and the molar extinction coefficient, ${\varepsilon}_{\lambda}^{AD}$, were determined using the Scott equation. The values of the charge-transfer transition frequency, ${\vu}_AD$ and $K_c{AD}$ correlated well respectively with the ionization potentials of the fused rings of Series Ⅰ or of the compounds of Series II and with the values of ${\sigma}_p$, the Hammett constants of the Series II substituents. trans-4-N,N-Dimethylaminostilbene and trans-4-nitrostilbene were found to be able to participate in electron transfer reaction with TCNQ forming the corresponding anion radical, TCNQ$^-$:

The Effect of Pressure and Temperature on the Durene-Iodine Charge Transfer Complex in n-Hexane (듀렌과 요오드 사이의 전하이동착물에 대한 압력과 온도의 영향)

  • Oh Cheun Kwun;Jeong Rim Kim
    • Journal of the Korean Chemical Society
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    • v.27 no.1
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    • pp.9-17
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    • 1983
  • The effect of pressures and temperatures on the stabilities of the durene-iodine charge transfer complex have been investigated through ultraviolet spectrophotometric measurements in n-hexane. The stabilities of complexes were measured at 25, 40 and $60^{\circ}C$ under $1{\sim}1600$ bars. The equilibrium constant of the complex was increased with pressure and decreased with temperature raising. The absorption coefficient was increased with both pressure and temperature. Changes of volume, enthalpy, free energy and entropy for the formation of complexes were obtained from the equilibrium constants. The red-shift observed at a higher pressure, the blue-shift at a higher temperature, and the relation between pressure and oscillator strength were discussed by means of thermodynamic functions.

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Photophysical Properties of Chlorotriethylphosphinegold(I)

  • Kang, Jun-Gill;Jeong, Yong-Kwang;Oh, Sung-Il;Kim, Hyun-Jun;Park, Chang-Moon;Tiekink, Edward R.R.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.8
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    • pp.2151-2157
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    • 2010
  • Spectroscopic and quantum mechanical studies of the Et3PAuCl complex were performed to characterize the effect of aurophilicity on the optical properties. When excited with UV light at low temperature, the crystalline complex produced a deep luminescence in both the blue (high-energy) and red (low-energy) regions of the spectrum. The intensity of the low-energy luminescence was markedly reduced in the powdered state and quenched in the solution state. Time-dependent density functional theory (TD-DFT) calculations on electronic structures of both the ground and excited states of aggregates $[Et_3PAuCl]_n$ (n = 1 - 3) indicated that the low-energy luminescence was attributable to Au-centered transitions, which are significantly affected by aurophilic interactions. By contrast, the high-energy luminescence appeared to be independent of the state of the complex and was strongly associated with the charge transfer from Cl to Au.

The Effect of Pressure and Temperature on the Mesitylene-Iodine Charge Transfer Complex in n-Hexane (고압, 고온 유체의 물성연구. 메시틸렌과 요오드 사이의 전하이동착물에 대한 압력과 온도의 영향)

  • Oh Cheun Kwun;Jong Gi Jee;Jeong Rim Kim
    • Journal of the Korean Chemical Society
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    • v.24 no.6
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    • pp.405-412
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    • 1980
  • The effect of pressures and temperatures on the stabilities of the mesitylene-iodine charge transfer complex have been investigated through ultraviolet spectrophotometric measurements in n-hexane. The stabilities of complexes were measured at 25, 40 and $60^{\circ}C$ under 1∼1600 bars. The equilibrium constant of the complex was increased with pressure and decreased with temperature raising. The absorption coefficient was increased with both pressure and temperature. Changes of volume, enthalpy, free energy and entropy for the formation of complexes were obtained from the equilibrium constants. The red-shift observed a higher pressure, the blue-shift at a higher temperature and the relation between pressure and oscillator strength were discussed by means of thermodynamic functions.

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