• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.355-360
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• 1984

A new absorption spectrum observed from dilute aqueous solutions of methylene blue$(MB^+)$ and tetraphenylborate(TPB$^-$) ions was investigated by spectrophotometry. The species responsible for the spectrum can be a charge-transfer complex formed between the two, univalent, and poorly hydrated ions in order to minimize the disturbance to the water structure. However, as the absorption band of MB$^+$ is split into two bands with exciton splitting of about 2,000 cm$^{-1}$, the formation of double ion-pair, (MB-TPB)$_2$ appears to be more favorable than the charge transfer complex.

• Journal of the Korean Chemical Society
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• v.19 no.2
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• pp.73-84
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• 1975

The effect of pressures and temperatures on the stabilities of the toluene-iodine charge transfer complex have been investigated through ultraviolet spectrophotometric measurements in n-hexane. The stabilities of complexes were measured at $25~60{\circ}C$ under 1~1,200 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.

• Bulletin of the Korean Chemical Society
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• v.6 no.2
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• pp.74-79
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• 1985

The stabilities of the charge transfer complexes of pentamethyl benzene with iodine in n-hexane have been investigated by UV-spectrophotometric measurements at 25, 40 and 60$^{\circ}C$ up to 1600 bars. The equilibrium constant of the complex formation was increased with pressure while being decreased with temperature raising. Changes of volume, enthalpy, free energy and entropy for the formation of the complexes were obtained from the equilibrium constants. The red-shift at higher pressure, the blue-shift at higher temperature, and the relation between pressure and oscillator strength have been discussed by means of thermodynamic functions. In comparison with the results in the previous studies, the absolute values of ${\Delta}$V at each temperature were increased with the number of methyl groups of polymethyl benzene. However, it can be seen that both ${\Delta}$H and ${\Delta}$S show extreme behaviors in durene near atmospheric pressure but they are negatively increased with the number of methyl groups near 1600 bar. This order of the thermodynamic parameters may be a measure of the relative basicities of polymethyl benzenes toward iodine under each pressure, and these phenomena are explained in terms of a positive inductive effect and a steric hindrance effect of the polymethyl benzene molecule.

• Journal of the Korean Chemical Society
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• v.17 no.1
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• pp.1-9
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• 1973

The purpose of this paper is to investigate the mechanism of Diels-Alder reaction by assuming pseudo molecular complex (PMC) which has characters both of ionic and radical bonds. We treated this complex quantum-chemically as an intermediate between the configuration without charge transfer (radical bond character) and the configuration corresponding to the charge transfer from Diene (R) to Dienophile (S) (ionic bond character). The wave function for the complex could be expressed as: ${\psi}_{complex} = {\psi}(R,S) +{ \rho}{\psi}(R^+,S^-)$ where ${\rho}$ is the extent of charge transfer which is a constant to measure the ionic character of PMC. It has been noticed that${\rho}$is related to the difference between Fr + Fr' and Fs + Fs' in free valence (F) when R is united to S through atom r in R to atom s in S and atom r' in R to atom s' in S, That is, ${\rho}{\alpha}$ ${\Delta}F = (Fr + Fr') - (Fs + Fs')$. We have calculated ${\Delta}F$values for more than forty Diels-Alder reactions. The calculated values of ${\Delta}F$ is reversely proportional to the values of Brown's paralocalization energy (Lp) as well as Dewar's differences of delocalization energy$({\Delta}Edeloc.)$ with good linearity. This approach also presents a way of predicting the possibility and the easiness of diene synthesis between any two conjugate compounds. According to the considerations, it could be concluded that Diels-Alder reaction takes place through the united ionic-radical mechanism rather than the separated ionic or radical mechanism.

• Bulletin of the Korean Chemical Society
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• v.9 no.6
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• pp.394-398
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• 1988

Unusually high reactivity was found in peptide bond formation between p-nitrobenzophenone oxime resin (I) ester and amino acid 4-(methylthio)phentyl (MTP) esters. A charge-transfer complex between the two phenyl rings of the oxime resin (I) and the incoming amino acid MTP esters was considered to be responsible to accelerate the aminolysis reaction of the peptide oxime resin ester. Several di-, tri-, and pentapeptide fragments for preparing enkephalin and glutathione oligomers were successfully prepared in short times.

• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.546-550
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• 2008

The title compound of nicotinato lead(II) complex [Pb$(C_5H_4NCOO)_2$] has been optimized at B3LYP/LANL2DZ and HF/LANL2DZ levels of theory. The calculated results show that the lead(II) ion adopts 2- coordinate geometry, which is the same as its crystal structure and different from the 4-coordinate geometry of isonicotinato lead(II) complex. Atomic charge distributions indicate that during forming the title compound, each nicotinic acid ion transfers their negative charges to central lead(II) ion. The electronic spectra calculated by B3LYP/LANL2DZ level show that there exist two absorption bands, which have some red shifts compared with those of isonicotinato lead(II) complex and the electronic transitions are mainly derived from intraligand $\pi$ -$\pi$ transition and ligand-to-metal charge transfer (LMCT) transition. CIS-HF method is not suitable for the system studied here. The thermodynamic properties of the title compound at different temperatures have been calculated and corresponding relations between the properties and temperature have also been obtained. The second order optical nonlinearity was calculated, and the molecular hyperpolarizability was $1.147754{\times}10^{-30}$ esu.

• Korean Journal of Fisheries and Aquatic Sciences
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• v.11 no.4
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• pp.205-211
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• 1978

The effect of phenol derivatives (guaiacol, vanillin, o-vanillin, eugenol) and catechol derivatives (pyrogallol, resoicinol) to enhance the volumetric oxygen transfer coefficient, in the aerobic fermentation was studies. Guaiacol, vanillin, o-vanillin, pyrogallol and resorcinol revealed to enchance the volumetric oxygen transfer coefficient, and eugenol had no such ability. The enhancement of the oxygen transfer ability is probably due to the formation of the charge transfer complex by the derivatives and oxygen molecules.

• Journal of the Korean Applied Science and Technology
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• v.12 no.2
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• pp.137-143
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• 1995

Octadecyltrimethylammonium-TCNQ(1:1) complex was synthesized by the reaction of LiTCNQ with octadecyltrimethylammonium bromide and the reaction product was identified with FT-IR and UV/Vis spectroscopies. In order to prepare the LB films, ${\pi}-A$ isotherm characteristics of octadecyltrimethylammonium-TCNQ(1:1) complex were investigated. The LB films of octadecyltrimethylammonium-TCNQ(1:1) complex were formed on various substrates and the formation of ultrathin films of octadecyltrimethylammonium-TCNQ(1:1) complex was confirmed by using FT-IR and UV-Vis spectroscopies.

• Journal of the Korean Chemical Society
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• v.38 no.8
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• pp.598-602
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• 1994

Light-induced electron transfer reaction within binuclear complex $(NC)_5FeII-L-CoIII(NH_3)_5$ was studied with steady-state photolysis and the rate constants were measured for various bridging lignands. klight and quantum yields for BP, PHEN, DAP having conjugation between metal binding sites were about $3{\times}10^{-2} sec^{-1}$ and 1, and for BPEA having no conjugation were about $2{\times}10^{-4} sec^{-1}$ and 0.03. Light-induced electron transfer reaction within binuclear complex was proved to be the chemical mechanism which had charge transfer excited state MLCT*.

• Bulletin of the Korean Chemical Society
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• v.18 no.6
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• pp.628-631
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• 1997

The preparation and characterization of $Co(dmppz)_2(3,6-dbq)_2$ (dmppz=1,4-dimethylpiperazine; 3,6-dbq=3,6-di-tert-butyl-1,2-quinone) are established. Temperature-dependent magnetic moments (100-400 K), variable-temperature IR, and electronic spectra are presented to show that the title complex exhibits an equilibrium via a catechol to cobalt intramolecular electron transfer. At temperatures below 350 K, the charge distribution of the complex is $Co^Ⅲ(dmppz)_2(3,6-dbsq)(3,6-dbcat)$ (3,6-dbsq=3,6-di-tert-butyl-1,2-semiquinonato; 3,6-dbcat=3,6-di-tert-butylcatecholato) whereas at the temperature beyond 390 K, the complex is predominantly Co^Ⅱ(dmppz)_2(3,6-dbsq)_2$ form in the solid state. At the temperature range of 350-390 K a mixture of Co(Ⅲ) and Co(Ⅱ) redox isomers exist at equilibrium. The transition temperature (Tc) of Co(Ⅲ)/Co(Ⅱ) in solution is approximately 50° lower than that in the solid state. In particular, thermal analysis on solid sample of the complex discloses that the transition for the Co(Ⅲ)/Co(Ⅱ) is accompanied by the change in heat content of 12.30 kcal/mol.