• Journal of the Korean Chemical Society
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• v.51 no.4
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• pp.339-345
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• 2007

Urea reacts with PtCl2, H2[PtCl6]·6H2O, H2[IrCl6] and Ni(CH3CO2)2 in aqueous solution at high temperature (60-80 °C) yielding [PtCl2(Urea)]·2H2O (1), (NH4)2[PtCl6] (2), (NH4)2[IrCl6]·H2O (3) and [Ni2(OH)2(NCO)2(H2O)2] (4) complexes, respectively. In complex 1, urea coordinates to Pt(II) as a neutral bidentate ligand via amido nitrogen atoms. In complexes 2, 3 and 4 it seems that the coordinated urea molecules decompose during the reaction at high temperature and a variety of reaction products are obtained. All complexes were isolated in moderate yields as dark green (1), yellow (2), pale brown (3) and faint green (4) precipitates, respectively. The reaction products were characterized by their microanalysis, IR, 1H and 13C NMR spectra as well as thermal analysis. General mechanisms describing the formation of these complexes were suggested.

• Bulletin of the Korean Chemical Society
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• v.29 no.3
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• pp.627-640
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• 2008

The geometrical structures, atomic charges, and relative energies of tetracoordinated Pd complexes [PdCl3Z (Z = Cl-, Br-, OH?-, H2O, NH3, PH3), PdCl2Z2 (Z = Br-, OH?-, H2O, NH3, PH3), PdZ?2X (Z = Cl-, OH?-, H2O, NH3, PH3; X = oxalate, O2-?CCO2-), and PdZ2Y (Z = Cl?-, OH?-, H2O, NH3, PH3; Y = succinate, CO2-?CHCHCO2-?)] and the ligand exchange reactions of the Pd complexes were investigated using the ab initio second order Mller-Plesset perturbation (MP2) and Density Functional Theory (DFT) methods. The geometrical characteristics of the tetracoordinated Pd(II) complexes with mono- and bidentate ligands, the effects of the atomic charges for the charged and uncharged ligands, the (dz2-p ) interactions between the dz2-orbital of Pd(II) and the p -orbital of bidentates, and the relative stabilities between the isomers of PdCl2Z2 and PdZ2Y were investigated in detail. The potential energy surfaces for the ligand exchange reactions used for the conversions of {[PdCl2(NH3)2] + H2O} to {[PdCl(NH3)2(H2O)]+ + Cl?-?} and {[PdCl2(PH3)2] + H2O} to {[PdCl(PH3)2(H2O)]+ + Cl?-?]} were investigated. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes were also examined quantitatively.

• Journal of the Mineralogical Society of Korea
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• v.24 no.2
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• pp.73-82
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• 2011

X-ray absorption spectroscopy (XAS) study was conducted using arsenite-sorbed two-line ferrihydrite to investigate the mechanism of surface interactions between two-line ferrihydrite and As(III) (arsenite) which are ubiquitous in nature. The two-line ferrihydrite used was synthesized in the laboratory and the study was undertaken at pHs 4 and 10 to compare the difference in mechanisms of surface interaction between acidic and alkaline environments. The effect of arsenite-adsorbed concentrations on surface complexation was investigated at each pH condition as well. From the results of XAS analyses, the structural parameters of arsenite in the EXAFS revealed that the coordination number and distanceof As-O were 3.1~3.3 and 1.74~1.79 ${\AA}$, respectively, which indicate that the unit structure of arsenite complex formed on the surface of two-line ferrihydrite is $AsO_3$. The dominant structures of As(III)-Fe complex were examined to be bidentate binuclear comer-sharing ($^2C$) and the mixture of bidentate mononuclear edge sharing ($^2E$) and $^2C$ appeared as well. At pH 4, arsenite complex showed different structures on the surface of two-line ferrihydrite, depending on the adsorbed concentrations. At pH 10, on the contrary, the surface structures of arsenite complexes were interpreted to be almost identical, irrespective of the adsorbed concentrations of arsenite. Consequently, this microscopic XAS results support the results of macroscopic adsorption experiments in which the surface interaction between arsenite and two-line ferrihydrite is significantly influenced by pH conditions as well as arsenite concentrations.

• Journal of the Korean Chemical Society
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• v.56 no.2
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• pp.217-227
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• 2012

Syntheses of some novel oxomolybdenum(V) and dioxomolybdenum(VI) complexes with an azo dye methoxyphenolazoantipyrine (HL) derived from 4-aminoantipyrine and 2-methoxyphenol are reported. The complexes have been characterized by elemental analyses, molar conductance, magnetic susceptibility data, IR, UV-Vis, $^1H$ NMR, EPR and FAB mass spectral studies. The physicochemical studies and spectral data indicate that HL acts as a bidentate chelating ligand. The complexes have the general formulae [$MoO(HL)XCl_2$] and [$MoO_2(HL)XCl$],where X=Cl, NCS or $NO_3$. All the complexes are found to have distorted octahedral geometry. Structural and morphological characterization of the complexes [$MoO(HL)Cl_3$](1) and [$MoO_2(HL)Cl_2$](4) before and after gamma ray irradiation,was performed by X-ray diffraction and scanning electron microscopy( SEM).The ligand and the complexes were screened for their possible antimicrobial activities.

• Bulletin of the Korean Chemical Society
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• v.26 no.12
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• pp.1965-1968
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• 2005

Extended H$\ddot{u}$ckel molecular calculations have been used to analyze how the magnitude of exchange coupling is influenced by the structural distortions in a series of dinuclear six-coordinate copper(II) complexes bridged by the planar bis-bidentate oxalate anion. Copper(II) ions have distorted octahedral surroundings, one being axially elongated and the other compressed. The magnetic interaction is strong in the former complexes and very weak in the latter. This is interpreted as resulting from a switching of magnetic spin orbitals due to the structural distortions (bond elongation or compression) of the copper sites.

• Journal of the Korean Society of Industry Convergence
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• v.3 no.1
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• pp.77-82
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• 2000

The stereoselective ligand exchange reaction of trans-$[Co(SS-epm)Cl_2]^+$ and racemic propane-1,2-diamine (rac-pn) produces the complex that is identified as $[CO(N)_6]^{3+}$ type of $[Co(SS-epm)(pn)]^{3+}$ by absorption spectrum. It is conceivable that the reaction mechanism involves substitution and isomerization. The calculated and experimentally determined ratios of the complexed enantiomeric substrates at equilibrium were as follows: $[Co(SS-epm)(pn)]^{3+}$,calcd 32 % / 68 %, exptl 19 % / 81 % R-pn / S-pn. It has been shown that the employment of molecular mechanics calculations as a predictive tool may lead to the design of chiral complexes that may be applied to the separation of racemic mixtures of simple bidentate ligands.

• Bulletin of the Korean Chemical Society
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• v.29 no.1
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• pp.69-75
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• 2008

Tautomerism of pyrimidine base cytosine has been comparatively examined on nanoparticle and roughened plate surfaces of silver, gold, and copper by surface-enhanced Raman scattering (SERS). The SERS spectrum was found to be different depending on the metals and their substrate conditions suggesting the dissimilar population of various tautomers of cytosine on the surfaces. The ab initio calculations were performed at the levels of B3LYP, HF, and MP2 levels of theory with the LanL2DZ basis set to estimate the energetic stability of the tautomers with the metal complexes as well as the gas phase state. The amino group and N3-coordinated tautomer was predicted to be more favorable for bonding to Au, whereas the hydroxyl and N1-coordinated zwitter ionic form is most stable with Ag and Cu as a bidentate form from the DFT calculation. The binding energy with the Ag atom is calculated to be smaller than those with the Au and Cu atoms in line with the temperature-dependent SERS spectra of cytosine.

• Journal of the Korean Ceramic Society
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• v.45 no.2
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• pp.126-131
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• 2008

In this study, we prepared zirconia gel by the sol-gel method and investigated its photoluminescence properties by varying pyrolysis temperature. The addition of acetic acid into a Zr-alkoxide solution resulted in forming the bidentate ligands with Zr ions and producing a stable gel. At the pyrolysis temperature of $350^{\circ}C$, the zirconia nanocrystals with tetragonal structure gradually appeared in the gel. The PL intensity of the zirconia gel increased with increasing the pyrolysis temperature up to $350^{\circ}C$, but decreased above the temperature. Concurrently, its PL peak wavelength continuously shifted from ${\sim}440\;nm$ to ${\sim}550\;nm$ with the temperature. The PL characteristics of the zirconia gels were closely associated with decomposition of residual organic groups, the formation of the zirconia nanocrystals, and the tetragonal to monoclinic phase transformation.

• Journal of the Korean Chemical Society
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• v.22 no.2
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• pp.99-104
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• 1978

The synthesis of a bidentate secondary amine ligand, 2,2-bis(methylaminomethyl-2,3-dioxolane(methylaminomethyl)-1,3-dioxolane(mexo) and the preparation of dichloro and trans-R-cyclohexanediamine platinum(II) complexes of this ligand are reported. The structures of the ligand and complexes prepared have been elucidated via elemental analyses, nmr, electronic absorption, and CD spectra.

• Journal of Applied Biological Chemistry
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• v.49 no.3
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• pp.86-89
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• 2006

The novel tetranuclear nickel (II) complex is a high rate accelerator in promoting hydrolysis of phosphate diesters. Nickel-bound bis-nitrophenyl phosphate (BNPP) can be $10^4$ times more reactive than the unbound BNPP. The large rate of enhancements by the complex slightly under basic condition has shown high catalytic activity in phosphate diester cleavage. The bell-shaped pH-rate profile indicated that the nickel-oxide form of the tetranuclear complex or its kinetic equivalent was the active species for cleaving BNPP. The catalytic hydrolysis between tetranuclear nickel (II) complex and phosphate diester proceeds via the formation of bidentate coordination of the anionic phosphate to the Ni (II) atom. This reveals that the complex has the possibility as artificial nuclease.