• Title/Summary/Keyword: Charge transfer complexes

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Syntheses and Photofading of Intermolecular Charge-Transfer Complex Dyes of Phenothiazine and Quinonoid Compounds (Phenothiazine과 Quinone계 분자간 전하 이동형 색소의 합성 및 광 퇴색)

  • 김성훈;이순남;임용진
    • Textile Coloration and Finishing
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    • v.4 no.2
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    • pp.64-68
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    • 1992
  • The charge-transfer(CT) complexes derived from phenothiazine as donor and quinonoid compounds as accepters were evaluated as coloring matter. Light fastness of the intermolecular charge-transfer(CT) complex dyes as well as absorption wavelength is an important factor when the complexes are applied to coloring matters. The photofading mechanism of CT complex dyes of phenothiazine and accepters were examined. The addition of effective radical scavenger, antioxidant and photostabilizer gave a remarkable enhancement of the photostability of CT dyes.

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Spectrophotometric Determination of Antihistaminics by using Iodine as Electron Acceptor (요오드를 전자수용체로 한 항히스타민제의 분광학적 분석)

  • Moon, Hong-Seob;Baik, Chai-Sun
    • YAKHAK HOEJI
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    • v.33 no.3
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    • pp.141-148
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    • 1989
  • The weak UV absorbing antihistaminics such as chlorpheniramine, triprolidine, tripelennamine and diphenhydramine were analyzed by charge-transfer spectrophotometric method. The results obtained are summarized as folows. It was possible to determine a weak UV absorbing antihistaminics using the intense charge-transfer UV bands in chloroform. Charge transfer complexes were formed in a 1:1 ratio between antihistaminics and iodine in chloroform. Linear relationship was found between absorbance and concentration in the range of $1.0\;{\times}\;10^{-5}M-5.0\;{\times}\;10^{-5}M$ for chlorpheniramine( ${\varepsilon}\;=\;2.082\;{\times}\;10^4$) and tripelennamine ( ${\varepsilon}\;=\;1.578\;{\times}\;10^4$), $1.0\;{\times}\;10^{-5}M-8.0\;{\times}\;10^{-5}M$ for triprolidine ( ${\varepsilon}\;=\;1.120\;{\times}\;10^4$) and $1.0\;{\times}\;10^{-5}M-1.0\;{\times}\;10^{-4}M$ for diphenhydramine ( ${\varepsilon}\;=\;9.900\;{\times}\;10^3$). Charge transfer complexes of chlorpheniramine, triprolidine and tripelennamine have absorption maxima at 293 nm and complex form of diphenhydramine has absorption maximum at 270 nm. By UV, IR spectra, it could be inferred that CT-complexes were formed by interaction between the basic nitrogen of antihistaminics as electron donor (non bonding electron) and iodine as electron acceptor (${\sigma}$ bonding electron).

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Photoinduced Charge-Transfer Association of Tetracyanoquinodimethane with Aminobiphenyls

  • Kim, Yong-Hee;Jung, Sang-Don;Chung, Myung-Ae;Song, Ki-Dong;Cho, Dae-Won
    • Bulletin of the Korean Chemical Society
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    • v.29 no.5
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    • pp.948-952
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    • 2008
  • The molecular association of acceptors with electron donors is studied in the highly-polar solvent $CH_3CN$. Tetracyanoquinodimethane (TCNQ) forms a stable charge-transfer complex with donor molecules such as 4- aminobiphenyl (4-AB), benzidine (BD) and 2-aminobiphenyl (2-AB) with high association constants. The complexes of TCNQ with 4-AB or BD show new absorption bands at around 800 and 500 nm, which can be identified as reduced $TCNQ^{{\bullet}-}$ and $TCNQ^{2-}$ species, respectively. These bands grow quickly upon photoirradiation, implying that the charge-transfer complexes are easily formed in an excited state. Conversely, a small spectral manifestation of the charge transfer was observed in the case of 2-AB complex. It is demonstrated that the structural orientation between the geminate ion pairs could play an important role in building a stable complex.

The Physicochemical Properties on the Charge Transfer Complexes under High Pressure (고압하의 전하이동착물에 대한 물성론적 연구-사염화탄소 용액내에서 헥사메틸벤젠과 여러 전자받게들간의 전하이동착물 생성에 대한 압력과 온도의 영향)

  • Kwun Oh Cheun;Kim Myong Ja;Kim Se Kyung
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.335-342
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    • 1991
  • The effect of pressure and temperature on the stabilities of the charge transfer complexes of 1,3,5-trinitrobenzene, tetrachloro-p-benzoquinone and tetracyanoethylene with hexamethylbenzene in carbon tetrachloride has been investigated by spectrophotometric measurements. The equilibrium constants for the formation of the complexes were obtained at various temperature and pressure, and thermodynamic parameters for the formation of the charge transfer complexes are calculated from these values. The relative stabilities of charge transfer complexes with hexamethylbenzene increase in the order; 1,3,5-trinitrobenzene < tetrachloro-p-benzoquinone < tetracyanoethylene. This may be regarded as an order of relative acidity of these compounds in complexation with hexamethylbenzene and is explained in terms of the negative inductive effect of the ${\pi}$ acceptors. The red-shift at higher pressure, the blue-shift at higher temperature and the relation between pressure and oscillator strength are discussed on the basis of thermodynamic functions.

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Photoreactivity and Thermogravimetry of Copper(II) Complexes of N-Salicylideneaniline and Its Derivatives

  • Osman, Ahmed H.;Aly, Aref A.M.;El-Mottaleb, Mohamed Abd;Gouda, Gamal A.H.
    • Bulletin of the Korean Chemical Society
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    • v.25 no.1
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    • pp.45-50
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    • 2004
  • $Cu^{II}$-complexes of N-salicylideneaniline and its derivatives were not light sensitive in most solvents such as acetonitrile. A photo-decomposition occurred upon irradiation in halocarbon solvents such as $CHCl_3$. It has been suggested that such photoreactivity is attributed to the reactivity of charge-transfer to solvent (CTTS) excited state attained upon irradiation. A mechanism has been proposed to account for the results obtained. The complexes have been thermally analysed in nitrogen and static air using thermogravimetry (TG) and derivative thermogravimetry (DTG). The thermal degradation of the complexes proceeds in two or three stages. The kinetic parameters obtained from the Coats-Redfern and Horowitz-Metzger equations show the kinetic compensation effect.

The Thermodynamics of the Formation of Polymethylbenzene-Halogens Charge Transfer Complexes (Ⅰ) (폴리메틸벤젠과 할로겐사이의 전하이동착물생성에 관한 열역학적 연구 (제1보))

  • Oh Cheun Kwun;Jin Burm Kyong
    • Journal of the Korean Chemical Society
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    • v.25 no.1
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    • pp.1-6
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    • 1981
  • Ultraviolet spectrophotometric investigations were carried out on the systems of o-, m-and p-xylene with iodine in carbon tetrachloride. The results reveal the formation of one to one molecular complexes of the type, $C_6H_4(CH_3)_2{\cdot}I_2. $The equilibrium constants of complexes were obtained in consideration of that absorption maxima has the blue shift with the increasing temperatures according to the formation of the charge transfer complexes. The thermodynamic parameters, $ {\Delta}$H, $ {\Delta}$G and $ {\Delta}$S for the formation of the charge transfer complexes were calculated from these values. These results combined with previous study of this series indicated that the relative stabilities of the polymethylbenzene complexes with iodine increase in the order, Benzene < Toluene < o-Xylene < p-Xylene These results are supposed to be the influence resulted from increase of electron density by the positive inductive effect and the steric hindrance effect.

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The Physicochemical Properties on the Organic, Charge Transfer Complexes under High Pressure (고압하의 전하이동착물에 대한 물성론적 연구. 사염화탄소 용액내에서의 헥사메틸벤젠과 1,3,5-트리니트로벤젠과의 전하이동착물 생성에 대한 압력과 온도의 영향)

  • Oh Cheun Kwun;Myong Ja Kim
    • Journal of the Korean Chemical Society
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    • v.32 no.6
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    • pp.513-519
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    • 1988
  • The effect of pressure and temperature on the stabilities of hexamethylbenzene-1,3,5-trinitrobenzene charge transfer complex in carbon tetrachloride has been investigated by spectrophotometric measurements. The absorption spectra of charge transfer complexes were measured at 25, 40, $50^{\circ}C$ under 1, 200, 500, 1000, 1400 bar in this experiments. The equilibrium constants of the complex were increased with pressure and decreased with temperature rising. The absorption coefficients were increased with pressure and temperature. Change of volume, enthalpy, free energy and entropy for the formation of complexes were calculated 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 fuctions.

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Energy Transfer Pathway in Luminescent Lanthanide Complexes Based on Dansyl-N-methylaminobenzoic Acid through Intramolecular Charge Transfer State for Near Infrared Emission

  • Roh, Soo-Gyun;Baek, Nam-Seob;Kim, Yong-Hee;Kim, Hwan-Kyu
    • Bulletin of the Korean Chemical Society
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    • v.28 no.8
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    • pp.1249-1255
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    • 2007
  • We have investigated the photophysical properties of dansyl-N-methylaminobenzoic acid (DABAH) as a ligand and its lanthanide (Ln3+)-cored complexes (Ln3+-(DABA)3(terpy)) in order to determine the main energy transfer pathway for sensitized near infrared emission of Ln3+ ions (Ln3+ = Nd3+ and Er3+) in Ln3+- (DABA)3(terpy). The fluorescence spectrum of DABAH shows a large Stokes shift with increasing solvent polarity. This large Stokes shift might be due to the formation of a twisted intramolecular charge transfer (TICT) state, as demonstrated by the large dipole moment in the excited state. It is in good agreement with the result that the phosphorescence even in the Gd3+-cored complex based on the DABAH ligand was not observed, maybe due to the highly forbidden character of the S1 → T1 transition in the DABAH ligand. A short decay component (ca. 1 ns) was observed in Er3+-(DABA)3(terpy) whereas the fluorescence lifetimes of DABAH and its Gd3+-(DABA)3(terpy) are observed about ~10 ns. The short component could be originated from the energy transfer process between the ligand and the Ln3+ ion. Based on the fluorescence of DABAH its Ln3+- (DABA)3(terpy), the sensitization of Ln3+ luminescence in the Ln3+-(DABA)3(terpy) takes place by the energy transfer via the TICT state of DABAH in the excited singlet state rather than via the excited triplet state.