• Journal of the Korean Chemical Society
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• v.38 no.2
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• pp.122-128
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• 1994

Macrocyclic ligand has been known to selectively bind with metal ions so that ability applied for the transport of metal ions across the emulsion liquid membrane in this study. The metal ions are transproted from the source phase to the receiving phase by the carrier of the organic phase. Several factors involved in the transport of metal ions acrose the emulsion membrane we reported here and these factors provided the informations for the selective seperation of some metal ion. Stability constants for cation-macrocyclic ligand and metal ion-anion receiving phase interaction are examined as parameters for the prediction of metal ion transport selectivities. $Pb^{2+}$ was transported higher rates than the other metal ions in the mixture solution. The interaction of metal ion to anion in receiving phase is important. $S_2O_3^{2-}$- in replacement of $NO_3^-$ in the receiving phase enhances the transport of $Pb^{2-}$since $Pb^{2-}-S_2O_3^{2-}$interaction is greater than $Pb^{2+}-NO_3^-$ interaction.

• Analytical Science and Technology
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• v.17 no.2
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• pp.91-97
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• 2004

Cryptand ion exchange resins were synthesized with 1-aza-15-crown-5 macrocyclic ligand attached to styrene divinylbenzene (DVB) copolymer with crosslink of 1%, 2%, 5% and 10% by substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, and IR-spectrum. The effects of pH, time, dielectric constant of solvent and crosslink on adsorption of uranium ($UO{_2}^{2+}$) ion were investigated. The uranium ion was showed fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order uranium ($UO{_2}^{2+}$), magnesium ($Mg^{2+}$), neodymium ($Nd^{3+}$) ion. The adsorption was in order of 1%, 2%, 5%, and 10% crosslink resin and adsorption of resin decreased in proportion to order of dielectric constant of solvents.

• Applied Chemistry for Engineering
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• v.19 no.3
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• pp.304-309
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• 2008

Cryptand series ion exchange resins were synthesized with 1-aza-12-crown-4 macrocyclic ligand attached to styrene (4 series dangerous matter) divinylbenzene (DVB) copolymer with crosslink of 1％, 2％, 4％ and 8％ by a substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, electron micrograph, and IR-spectrum. The effects of pH, time, dielectric constant of solvent and crosslink on adsorption of uranium (${UO_2}^{2+}$) ion were investigated. The uranium ion showed a fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order uranium (${UO_2}^{2+}$) > nickel ($Ni^{2+}$) > gadolinium ($Gd^{3+}$) ion. The adsorption was in order of 1％, 2％, 4％, and 8％ crosslinked resin and adsorption of resin decreased in proportion to order of dielectric constant of solvents.

• Applied Chemistry for Engineering
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• v.22 no.6
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• pp.697-702
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• 2011

Ion exchange resins have been synthesized from chloromethylated styrene-1,4-divinylbenzene (DVB) with 1%, 2%, 5% and 15%-crosslinkage and macrocyclic ligand of $OenNdien-H_4$ by copolymerization. The adsorption characteristics of uranium (${UO_2}^{2+}$), potassium ($K^+$) and neodymium ($Nd^{3+}$) metallic ions have been investigated. The synthesis of these resins was confirmed by content of chlorine, element analysis, and IR-spectrum. The effects of pH, time, and crosslinkage on adsorption of metallic ions were also studied. The uranium ion showed the fast adsorption on the resins above pH 3. The optimum equilibrium time for the adsorption of metallic ions was about two hours. The adsorption selectivity determined in methanol solution was in increasing order uranium (${UO_2}^{2+}$) > potassium ($K^+$) > neodymium ($Nd^{3+}$) ion. Moreover, the adsorption was increased with the crosslinkage concentration in order of 1%, 2%, 5% and 15%-crosslinkage resin.

• Analytical Science and Technology
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• v.22 no.1
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• pp.92-100
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• 2009

Azacrown resins were synthesized by mixing 1-aza-12-crown-4 macrocyclic ligand into styrene (2th petroleum in 4th class hazardous materials) divinylbenzene (DVB) copolymer with crosslinkage of 1%, 2%, 5% and 10% by substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, thermogravimetric analysis (TGA), surface area (BET), and IR-spectroscopy. The effects of pH, time, crosslinkage of resins and dielectric constant of solvent on adsorption of metal ions by resin adsorbent were investigated. Metal ions showed a great adsorption over pH 3 and adsorption equilibrium of metal ions was about two hours. In addition, adsorptive selectivity of metals on the resin in ethanol solvent was increased in the order of ${UO_2}^{2+}$ > $Ca^{2+}$ > $Sm^{3+}$ ion and adsorption of uranium ion was decreased with increase of crosslinkage such as 1%, 2%, 5% and 10% and was inversely proportional to the order of dielectric constant of solvents.

• Journal of the Korean Chemical Society
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• v.34 no.2
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• pp.143-158
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• 1990

Metal complexes were prepared by reacting uranium (Ⅵ), thorium (Ⅳ) and rare earth metal (Ⅲ) ions including Nd (Ⅲ), Sm (Ⅲ) and Ho (Ⅲ) with macrocyclic ligands including five crown ethers, nine crownands and one cryptand ligands, and subjected to NMR studies in order to examine coordination sites of the ligands and compositions of the complexes formed. Among the marcocyclic ligands, crown ethers and crownand ligands have shown down-field shifts of the methylene protons of the lcigands by forming stable complexes with all the metal ions and the differences of chemical shifts were decreased as increasing of the cavity-size of crown ethers for the same metal ions and decreasing of the atomic number of the rare earth metals for the same ligands. It has been found that crownand 22 gave a stable complex with uranium(Ⅵ) ion by the coordination through both oxygen and nitrogen atoms of the ligand whereas no complex was formed with the rare earth metal(Ⅲ) ions, which on the other hand were found to form stable complexes with cryptand 221. The rest of the crowand ligands have also been found to form stable complexes with uranium(Ⅵ) ion by coordinating through all the oxygen and nitrogen atoms of the ligands whereas no complexes were formed with the rare earth metal(Ⅲ) ions. It has also been shown by 1H-NMR study that uranium(Ⅵ), thorium(Ⅳ) and rare earth metal(Ⅲ) ions formed 1:1 complexes with the macrocyclic ligands except for thorium(Ⅳ) complex of 12C4 in which the mole ratio of metal to ligand is 1:2. More stable metal complexes show larger changes in chemical shifts of the coordinated ligand protons. Finally, the rare earth metal(Ⅲ) complexes of 18C6 have shown ligand exchange reaction with the solvent molecules in acetylacetone solution, which was not observed for the uranium (Ⅵ) complexes.

• Journal of the Korean Chemical Society
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• v.24 no.2
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• pp.139-145
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• 1980

High spin iron(II) complexes of 1,4,8,11-tetraazacyclotetradecane (cyclam), a macrocyclic ligand, and 1,5,8,12-tetraazadodecane (3,2,3-tet), a noncyclic ligand, have been prepared. The reaction of low spin $[Fe(cyclam)(CH_3CN)_2](ClO_4)_2$ with chloride ion in methanol produces high-spin $[Fe(cyclam)Cl]ClO_4$. Although $[Fe(cyclam)(CH_3CN)_2](ClO_4)_2$ is low spin, $[Fe(3,2,3-tet)(CH_3CN)_2](ClO_4)_2$ isolated in the present study is high spin. This difference is explained in terms of the smaller constrictive effect exerted by the noncyclic ligand than the cyclic ligand. The isolation of $[Fe(cyclam)Cl]ClO_4$ provides evidences against the current view that the presence of either unsaturation or substituents on the macrocyclic ligands is necessary for the successful preparation of high spin five-coordinate iron (II) complexes. Reactions of $[Fe(cyclam)Cl]ClO_4\;and\;[Fe(3,2,3-tet)(CH_3CN)_2](ClO_4)_2$ with carbon monoxide yield low spin six-coordinate $[Fe(cyclam)Cl(CO)]ClO_4\;and\;[Fe(3.2,3-tet)(CH_3CN)(CO)](ClO_4)_2$, respectively.

• Bulletin of the Korean Chemical Society
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• v.25 no.7
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• pp.977-982
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• 2004

The reaction of $cis-[Cr([14]-decane)(OH_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = benzoate(bz) or chlorobenzoate(cbz)} leads to a new compound $[Cr([14]-decane)(bz)_2]ClO_4$ or $[Cr([14]-decane)(cbz)_2]ClO_4$. These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. The crystal structure of $[Cr([14]-decane)(cbz)_2]^+$ was determined. The complex shows a distorted octahedral coordination environment with the macrocycle adopting a folded cis-V conformation. The angle $N_{axial}-Cr-N_{axial}$ deviates by $14.5^{\circ}$ from the ideal value of $180^{\circ}$for a perfect octahedron. The bond angle cis-O-Cr-O between the Cr(III) ion and the two carboxylate oxygen atoms of the monodentate p-chlorobenzoate ligands is close to 90$^{\circ}$. The FAB mass spectra of the $cis-[Cr([14]-decane)(La)_2]ClO_4$ display peaks due to the molecular ions $[Cr([14]-decane)(bz)_2-H]^\;,\;[Cr([14]-decane)(cbz)_2-2H]^$ at m/z 578, 646, respectively.

• Bulletin of the Korean Chemical Society
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• v.26 no.9
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• pp.1395-1402
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• 2005

The reaction of cis-[Cr([14]-decane)$(OH)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = acetylacetonate (acac), oxalate (ox) or malonate (mal)} leads to a new cis-[Cr([14]-decane)(acac)]$(ClO_4)_2{\cdot}(1/2)H_2O\;(1),\;cis-[Cr([14]-decane)(ox)]ClO_4{\cdot}(1/2)H_2O\;(2)\;or\;cis-[Cr([14]-decane)(mal)]ClO_4{\cdot}(1/4)H_2O\;(3)$. These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)(acac)]$(ClO_4)_2{\cdot}(1/2)H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two acetylacetonate-oxygen atoms are bonded to the chromium(III) ion in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by $11^{\circ}$ from the ideal value of $180^{\circ}$ for a perfect octahedron. The bond angle O-Cr-O between the chromium(III) ion and the two acetylacetonate-oxygen atoms is close to $90^{\circ}$. The bond lengths of Cr-O between the chromium and the acetylacetonate-oxygen atoms are 1.950(3) and 1.954(2) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 1560 {ν (C=O)}, 1710 {${\nu}_{as}$(OCO)} and 1660 $cm^{-1}$ {${\nu}_{as}$(OCO)} attributed to the acac, ox and mal auxiliary ligands stretching vibrations, respectively.

• Bulletin of the Korean Chemical Society
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• v.26 no.4
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• pp.634-640
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• 2005

The reaction of cis-[Cr([14]-decane)(OH$_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = citrate(cit)} leads to a new dimeric complex cis-[{Cr([14]-decane)($\mu$-cit)}$_2](ClO_4)_2$. This binuclear complex has been structurally characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[{Cr([14]-decane)($\mu$-cit)})($_2]^+$ reveals that each chromium has a distorted octahedral coordination environment and citrato ligands are monodentate to the two chromium atoms via the carboxyl groups. For dimeric complex the bridging geometry is as follows: Cr$\ldots$Cr = 7.361 $\AA$; Cr-O(average) = 1.958 (8) $\AA$; Cr-N range = 2.108 (9)-2.147(9) $\AA$; N(1)-Cr-N(3) (equatorial position) = 98.0(4)$^{\circ}$; N(2)-Cr-N(4) (axial position) = 166.4(4)$^{\circ}$; O(1)-Cr-N(2) = 98.1(4)$^{\circ}$; O(3)-Cr-N(4) = 96.6(3)$^{\circ}$; O(1)-Cr-O(3) = 90.4$^{\circ}$. The FAB mass spectrum of the dimeric complex displays peak due to the molecular ions cis-[{Cr([14]-decane)($\mu$-cit)})($_2]^+$ at m/z 1053.