• Journal of the Korea Academia-Industrial cooperation Society
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• v.7 no.4
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• pp.733-737
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• 2006

In this paper, we report the coordination state and structure of $Zn(cyclam)Cl_{2})$ complex that was studied by the Raman spectrum and conductivity method. The complex of zinc(II) ion with 1,4,8,11-tetraazacyclotetradecane(cyclam) ligand is formed in aqueous solution. According to the Raman spectrum of $Zn(cyclam)Cl_{2})$ complex, $H_{2}O$ molecule and $Cl^{-}$ ion compete for the trans coordination site of zinc(II) ion. We also have investigated the competition effect of $H_{2}O$ molecule and $Cl^{-}$ ion by the conductivity method. On addition of 1,4,8,11-tetraazacyclotetradecane(cyclam) ligand to the aqueous $ZnCl_{2}$ solution, 2: 1 electrolyte is changed to 1:1 electrolyte. We suggest the possibility of elimination of heavy metal because of the affinity effect of macrocyclic polyamine(1,4,8.11-tetraazacyclotetradecane) for the heavy metal,.

• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.205-211
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• 1992

The $2{\nu}_{C=0}$ + amide III combination band spectrum of acetamide (AA) was obtained in very dilute solutions of AA+lanthanide shift reagents (LSR) in carbon tetrachloride over the range of $15^{\circ}$ to $45^{\circ}C$. It was found that only 1 : 1 AA-LSR complex is formed by the interaction between carbonyl oxygen of AA and central metal ion(Ln(Ⅲ)) in LSR. The thermodynamic parameters for Ln(III)${\cdot}$O=C bond were determined by computer analysis of concentration and temperature dependent spectra. ${\Delta}H^{\circ}$ for the coordination of AA to Eu$(dpm)_3$, Yb$(dpm)_3$, and Pr$(dpm)_3$ have been found to be -39.1, -28.4, and -25.5 kJ/mol, respectively. It has shown that this type of ion-dipole interaction is more than twice stronger compared to the dipole-dipole interaction in the amide linkage, and largely depending on the steric hindrence effect by the bulky dpm groups around central metal ion (Ln(III)) rather than the ionic potential effect of central metal ion itself.

• Bulletin of the Korean Chemical Society
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• v.33 no.4
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• pp.1349-1352
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• 2012

• Bulletin of the Korean Chemical Society
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• v.23 no.6
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• pp.824-829
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• 2002

New di-N-cyanomethylated tetraaza macrocycle 2.13-bis(cyanomethyl)-5.16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^7.12$]docosane $(L^2)$ has been prepared by the reaction of 3, 14-dimethyl-2,6,13,17-tetraazatricyclo $(L^1)$ with bromoacetonitrile. The square-planar complexes $[ML^2](ClO_4)_2(M=Ni(II)$ or Cu(II) can be prepared by the reaction of $L^2$ with the corresponding metal ion in acetonitrile. The cyanomethyl groups of $[ML^2](ClO_4)_2readily$ react with water to $yield[ML^3](ClO_4)_2$ containing pendant amide groups. The trans-octahedral complexes $[ML^4](ClO_4)_2$, in which two imidate ester groups are coordinated to the metal ion, can be also prepared by the reaction of $[ML^2](ClO_4)_2with$ methanol under mild conditions. The hydrolysis and alcoholysis reactions of $[ML^2](ClO_4)_2are$ promoted by the central metal ion, in spite of the fact that the cyanomethyl group is not involved in intramolecular coordination. The reactions are also promoted by a base such as triethylamine but are retarded by an $acid(HClO_4).Interestingly$, the imidate ester groups of $[ML^4]^2$ are unusually resistant to hydrolysis even in 0.1 M $HCIO_4$ or 0.1 M NaOH aqueous solution. Crystal structure of $[NiL^4](ClO_4)_2shows$ that the Ni-N (pendant imidate ester group) bond is rlatively strong; the Ni-N bond distance is shorter then the Ni-N(tertiary) distance and is similar to the Ni-N (secondary) distance.

• Journal of the Korean Chemical Society
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• v.53 no.3
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• pp.257-265
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• 2009

The structures and metal affinities of the binding configurations of $Cu^{+}$ and $Cu^{2+}$ to proline have been investigated using the hybrid three-parameter Density Functional Theory(DFT/B3LYP). We found that the metal-proline bonding and the energy ordering of several conformers were very different in $Cu^{+}$-proline and $Cu^{2+}$-proline. For $Cu^{+}$-proline, the ground state structure was found to have a bidentated coordination in which $Cu^{+}$ was coordinated to the carbonyl oxygen and imino group nitrogen of neutral proline. On the contrary, the ground state structure of $Cu^{2+}$-proline involves chelation between the two oxygens of the carboxylate group in a zwitterionic proline. The metal ion affinity of proline of the most stable $Cu^{+}$-proline complex was calculated as 76.0 kcal/mol at 6-311++G(d,p) level, whereas the $Cu^{2+}$ ion affinity of proline was calculated as 258.5 kcal/mol.

• Bulletin of the Korean Chemical Society
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• v.29 no.10
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• pp.1905-1910
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• 2008

The reaction of 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.0$0^{1.18}.0^{7.12}$]docosane ($L^1$) with formaldehyde in warm methanol yielded 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.$1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^7$) containing one 1,3-diazacyclohexane subunit. In methanol, $L^7$ readily reacts with $Cu^{2+}$ ion to form [$CuL^7(H_2O)$]$^{2+}$ which is extremely inert against methanolysis. In the solution containing $Ni^{2+}$ ion, however, $L^7$ reacts with methanol to yield [$NiL^3$]$^{2+}$ ($L^3$ = 2-(methoxymethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.$0^{1.18}.0^{7.12}$]- docosane), in which one N-$CH_2OCH_3$ pendant arm is appended. The copper(II) complex [$CuL^7(H_2O)$]- $(ClO_4)_2{\cdot}3H_2O\;(I{\cdot}3H_2O)$ has a severely distorted trigonal bipyramidal coordination geometry with a 4-5- 6-5 chelate ring sequence. The crystal structure of [$NiL^3$]$(PF_6)_2{\cdot}2H_2O$ (IIb) shows that the N-$CH_2OCH_3$ pendant arm is not coordinated to the metal ion in the solid state. In various solvents (S), however, the nickel(II) complex exists as a mixture of [$NiL^3$(S)]$^{2+}$, in which the N-$CH_2OCH_3$ group as well as S is coordinated to the metal ion, and [$NiL^3$]^{2+}.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3749-3754
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• 2013

Two 3D isomorphous and isostructural complexes, namely, $[Zn(BDOA)(bpy)(H_2O)_2]_n$ (1) and $[Cd(BDOA)-(bpy)(H_2O)_2]_n$ (2); (BDOA = Benzene-1,4-dioxyacetic acid, bpy = 4,4'-bipyridine) were synthesized under hydrothermal conditions and characterized by means of elemental analyses, thermogravimetric (TG), infrared spectrometry, and single crystal X-ray diffraction. Complexes 1 and 2 crystallize in the triclinic system, space group P-1 and each metal ion in the complexes are six-coordinated with the same coordination environment. In the as-synthesized complexes, $BDOA^{2-}$ anions link central metal ions to form a 1D zigzag chain $[-BDOA^{2-}-Zn(Cd)-BDOA^{2-}-Zn(Cd)-]_{\infty}$, whereas bpy pillars connect metal ions to generate a 1D linear chain $[-bpy-Zn(Cd)-bpy-Zn(Cd)-]_{\infty}$. Both infinite chains are interweaved into 2D grid-like layers which are further constructed into a 3D open framework, where hydrogen bonds play as the bridges between the adjacent 2D layers. Luminescent properties of complex 1 showed selectivity for $Hg^{2+}$ ion.

• Bulletin of the Korean Chemical Society
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• v.9 no.6
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• pp.368-376
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• 1988

Transition metal PSSA ionomers containing Co(II), Ni(II), Cr(III), Ru(III), and Rh(III) are investigated by IR, Far-IR, UV-Vis and DSC. Reliable IR Spectroscopic criteria are established for assessing the degree of ion-exchange of PSSA ionomers and the local structures around metal cations in them. In the hydrated transition metal PSSA ionomers, the ionic groups are solvated by water molecules and there is no significant interactions between sulfonate group and metal cations. The visible spectra indicated that metal cations are present as [M$(H_2O)_6$]$^{n+}$ with Oh symmetry. Their $T_g$ values increase as the extent of ionic site concentration increases, but there is no direct dependence of $T_g$ on the nature of metal cations or their oxidation states. Thus, the water content in PSSA ionomer is found to have dominant influence on $T_g$ of hydrated transition metal PSSA ionomers. Dehydration of the hydrated transition metal PSSA ionomers results in direct interaction between ionic groups and significant color changes of the ionomers due to the changes of the local structures around metal cations. On the base of spectral data, their local structures are discussed. In case of dehydrated 12.8 and 15.8 mol % transition metal PSSA ionomers, no glass transition is observed in 25-$250^{\circ}C$ region and this is believed to arise from the formation of highly crosslinked structures caused by direct coordination of sulfonate groups of metal cations. In the 6.9 mol % transition metal PSSA ionomers, the glass transition is always observed whether they are hydrated or dehydrated and this is though to be caused by the sufficient segmental mobility of the polymer backbone.

• Analytical Science and Technology
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• v.9 no.3
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• pp.221-234
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• 1996

Basic studies for the effective extraction of dibenzylammonium dibenzyldithiocarbamate(DBADBDC) complexes of Ag(I), Pd(II), Au(III) and Pt(IV) into chloroform have been conducted. The effects of pH on the extraction of ligand itself and metal cemplexes showed that DBADBDC itself was uniformly extracted in the pH range of 2~9 and metal complexes were effectively extracted at the pH range as follows. That is, Ag(I) : in an acidic aqua medium, Pd(II) : > 4, Au(III) : wide range, and Pt(IV) : > 3. The distribution ratio and extractabilities were obtained from the partition and extraction equilibria of metal-DBDC complexes between aqueous solution and chloroform. Ag(I) : log D=4.226 : E(%)=99.9% in the aqueous solution of pH 0, Pd(II) : log D=1.804 : E(%)=98.5% at pH 4~7, Au(III) : log D=3.755 : E(%)=99.9% at pH 2~10, and Pt(IV) : log D=0.165 : E(%)=57.2% at pH 8.0. And also mole ratio of metal ion to ligand in complexes were determined by mole ratio method : 1 : 1 for Ag(I) and 1 : 2 for Pd(II), Au(III) and Pt(IV). $Cl^-$ was included as a coordination species in complexes of Au(III) and Pt(IV). Besides, extraction mechanisms of compleses sere examined in the presence of chloride ion in an aquous solution, and extraction reactions and estraction constants could be proposed and calculated, respectively.

• Journal of the Korean Chemical Society
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• v.47 no.1
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• pp.26-30
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• 2003

The dinuclear $Ag_2[Phen]_2[S_2P(OPr)_2]_2$(phen=1,10-phenanthroline; Pr=propyl), was prepared by the reaction of bis(dipropyldithiophosphato) silver(I) complex with 1,10-phenanthroline ligand, and its structure was determined by X-ray crystallography. The two dipropyldithiophosphato ligands each bridge two silver atoms to form an eight-membered $Ag_2S_4P_2$ ring, while the 1,10-phenanthroline molecule coordinates to a silver atom to complete the local tetrahedral geometry for the metal ion. The Ag-S bond distances are 2.559(1) and 2.567(1)${\AA}$, and the Ag-N bond distances are 2.366(3) and 2.471(3)${\AA}$.