• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1467-1468
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• 2010

• Bulletin of the Korean Chemical Society
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• v.4 no.5
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• pp.219-223
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• 1983

Thianthrene cation radical perchlorate (1) reacted with N-free sulfonamides to give directly N-sulfonylsulfilimines (5a-5c) but reaction with N-alkylsulfonamides afforded, inter alia, 5-(2-thianthreniumyl) thianthrene perchlorate (6).

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.267-270
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• 2002

Photodissociations of o-, m-, and p-iodotoluene radical cations were investigated by using Fourier-transform ion cyclotron resonance (FT-ICR) spectrometry. Iodotoluene radical cations were prepared in an ICR cell by a photoionization charge-transfer method. The time-resolved one-photon dissociation spectra were obtained at 532 nm and the identities of $C_7H_7^+$ products were determined by examining their bimolecular reactivities toward toluene-$d_8$. The two-photon dissociation spectra were also recorded in the wavelength range 615-670 nm. The laser power dependence, the temporal variation, and the identities of $C_7H_7^+$ were examined at 640 nm. The mechanism of unimolecular dissociation of iodotoluene radical cations is elucidated: the lowest barrier rearrangement channel leads exclusively to the formation of the benzyl cation, whereas the direct C-I cleavage channel yields the tolyl cations that rearrange to both benzyl and tropylium cations with dissimilar branching ratios among o-, m-, and p-isomers. With a two-photon energy of 3.87 eV at 640 nm, the direct C-I cleavage channel results in the product branching ratio, [tropylium cation]/[benzyl cation], in descending order, 0.16 for meta >0.09 for ortho >0.05 for para.

• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.34-43
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• 1980

The reaction of thianthrene cation radical perchlorate with thioxanthene in acetonitrile gave thianthrene and dark reddish thioxanthylium ion instead of thioxanthene cation radical. Addition of aromatic nucleophiles such as anisole, aniline, N,N-diethylaniline, catechol, ethylbenzene, to the above mixture yielded the corresponding thioxanthenes with substituent at 9 position. Reactions with dibenzo-18-crown-6-ether, diphenylmercury, and triphenylphosphine gave similar products. However, reactions with aromatics with electron-withdrawing group were either too slow or inert to such a reaction.

• Journal of the Korean Magnetic Resonance Society
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• v.4 no.2
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• pp.82-90
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• 2000

Photoinduced charge separation of alkylphenothiazines in molecular assemblies such as positively, negatively and neutrally charged micelle interface results in the paramagnetic phenothiazine cation radical. This was studied as a model system for the light energy conversion into chemical energy. The photoproduced phenothaizne cation radical was identified and its amount was quantized with electron spin resonance (ESR). The microenvironment of photoproduced cation radical was studied with pulsed-ESR. Such a charge separation is enhanced by the optimization of various structural factors of the molecular assemblies. The structural factors of molecular assemblies have focused on the interface charge, interface structure with different headgroups and interfacial perturbation by disolving interface active organic additives.

• Bulletin of the Korean Chemical Society
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• v.9 no.2
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• pp.84-87
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• 1988

The Photophysical and photochemical properties of Ruthenium bipyridine with two long hydrocarbon chains, $[Ru(bipy)_2(dhbipy)]^{2+}$ and transient phenothiazine derivative cation radical $(PTD^+)$ in the cationic vesicle were studied. Transient absorption spectra of cation radical of phenothiazine derivative in the vesicle system containing the $Ru^{2+}$ complex, $[Ru(bipy)_2(dhbipy)]^{2+}$, (1) as sensitizer and phenothiazine derivative as electron donor was observed by XeCl excimer laser photolysis system. Thus the excited ruthenium complex would be quenched by phenothiazine derivative(PTD) reductively in the vesicle system. The quenching rate constant($K_Q$) of $Ru^{2+}$ with two long hydrocarbon chains in the vesicle by PTD was $9.6{\times}10^8M^{-1}S^{-1}$. The absorption decay kinetics showed that lifetime of phenothiazine derivative cation radical is a value in the 4-8m sec range.

• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1561-1565
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• 2012

The structures of the four lowest alanine conformers, along with their radical cations and the effect of ionization on the intramolecular proton transfer process, are studied using the density functional theory and MP2 method. The energy order of the radical cations of alanine differs from that of the corresponding neutral conformers due to changes in the basicity of the $NH_2$ group upon ionization. Ionization favors the intramolecular proton transfer process, leading to a proton-transferred radical-cation structure, [$NH_3{^+}-CHCH_3-COO{\bullet}$], which contrasts with the fact that a proton-transferred zwitterionic conformer is not stable for a neutral alanine in the gas phase. The energy barrier during the proton transfer process is calculated to be about 6 kcal/mol.

• Journal of the Korean Electrochemical Society
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• v.12 no.1
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• pp.54-60
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• 2009

The redox characteristics of 2-arylaldehydehydrazono-3-phenyl-5-substituted-2, 3-dihydro-1, 3, 4-thiadiazoles (1a-h) have been investigated in nonaqueous solvents such as 1, 2-dichloroethane (DCE), dichloromethane (DCM), acetonitrile (AN), Tetrahydrofuran (THF), and dimethylsulfoxide (DMSO) at platinum electrode. Through controlled potential electrolysis, the oxidation and reduction products of the investigated compounds had been separated and indentified. The redox mechanism had been suggested and proved. It had been found that all the investigated compounds were oxidized in two irreversible one-electron processes following the well-known pattern of The EC-mechanism; the first electron loss gives the corresponding cation-radical which is followed by proton removal from the ortho-position in the N-phenyl ring forming the radical. The obtained radical undergoes a second electron uptake from the nitrogen in the N = C group forming the unstable intermediate (di-radical cation) which undergoes ring closure forming the corresponding cation. The formed cation was stabilized in solution through its combination with a perchlorate anion from the medium. On the other hand, these compounds are reduced in a single two-electron process or in a successive two one-electron processes following the well known pattern of the EEC-mechanism according to the nature of the substituent; the first one gives the anion-radical followed by a second electron reduction to give the dianion which is basic enough to abstract protons from the media to saturate the (C = O) bond.

• Journal of Integrative Natural Science
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• v.2 no.1
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• pp.1-12
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• 2009

This miniaccount presents the selective examples of our recent discoveries in the photopolymerization of vinyl monomers using the organic initiators such as hydrosilanes, poly(hydroarylsilane)s, benzoin silyl ethers, and thianthrene cation radical. In the photopolymerization of vinyl monomers with silanes polysilanes, while the polymerization yields and polymer molecular weights of the poly(MMA)s containing the silyl moieties decreased, the TGA residue yields and intensities of SiH stretching IR bands increased as the mole ratio of the silanes over MMA increased. The hydroarylsilane and poly(hydroarylsilane) seemed to influence strongly on the photopolymerizaiton of olefinic monomers as both chain initiation and chain transfer agents. For the photohomopolymerization and photocopolymerization of MA and AA, the similar trends were observed. Benzoin silyl ethers and thianthrene cation radical also exhibit the photoinitiating ability in the photopolymerization of MMA.

• Bulletin of the Korean Chemical Society
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• v.17 no.8
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• pp.754-759
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• 1996

Ab initio Hartree-Fock and Becke 3-Lee-Yang-Parr (B3LYP) density functional theory calculations using 6-31G* basis set were carried out to study the vibrational spectra of anthracene neutral (h10 and d10) and radical cation (h10). We report results of the fundamental vibrational frequencies obtained on the basis of the calculations. The assignments of fundamentals show a one-to-one correspondence between the observed and calculated fundamentals.