• 대한화학회지
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• 제34권5호
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• pp.418-423
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• 1990

새로이 합성된 거대고리 리간드 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-trioxa cycloeicosane (NdienOdienH$_4$)와 이미 합성된 거대고리 리간드 1,12,15-triaza-3,4;9,10-dibenzo-5,8-dioxa cycloheptadecane (NdienOenH$_4$)와 1,15-diaza-3,4;12,13-dibenzo-5,8,11-trioxa cycloheptadecane (NenOdienH$_4$)를 25$^{\circ}C$ 수용액에서 전위차계를 이용하여 양성자 첨가반응의 평형상수를 구하였다. 또한 위의 세 가지 리간드 각각과 Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ)의 금속이온과의 착물을 합성하여 25$^{\circ}C$수용액에서 안정도 상수를 전위차법으로 구하였다. 그리고 위의 착물 수용액에 에틸렌 디아민용액을 가해 착물의 리간드 치환반응 속도상수를 분광광도법으로 측정하였다. 그리고 활성화에너지와 활성화파라메타(${\{Delta}H^{\neq}$, ${\{Delta}S^{\neq}$)를 구하여 이 반응계의 타당한 메카니즘을 제안하였다.

• 환경위생공학
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• 제22권3호
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• pp.77-87
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• 2007

The ion exchange resins have been synthesized from chlormethyl styrene - 1,4 - divinylbenzene(DVB) with 1%, 3%, and 5%-crosslinking and macro cyclic ligand of OenNen-$H_4$ by copolymerization method and the adsorption characteristics of uranium(VI), iron(II) and samarium(III) metallic ions have been investigated in various experimental conditions. 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 metallic ions 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 ${UO_2}^{2+}>Fe^{2+}>Sm^{3+}$ ion. The adsorption was in order of 1%, 3%, and 5% crosslink resin and adsorption of resin decreased in proportion to order of dielectric constant of solvent.

• 대한화학회지
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• 제62권6호
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• pp.427-432
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• 2018

The reaction of [$[Ni(L)]Cl_2{\cdot}2H_2O$ (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[$14,4,0^{1.18},0^{7.12}$]docosane) with 1,1-cyclohexanediacetic acid ($H_2cda$) yields mononuclear nickel(II) complex, [$Ni(L)(Hcda^-)_2$] (1). This complex has been characterized by X-ray crystallography, electronic absorption, cyclic voltammetry and thermogravimetric analyzer. The crystal structure of 1 exhibits a distorted octahedral geometry with four nitrogen atoms of the macrocycle and two 1,1-cyclohexanediacetate ligands. It crystallizes in the triclinic system P-1 with a = 11.3918(7), b = 12.6196(8), $c=12.8700(8){\AA}$, $V=1579.9(2){\AA}^3$, Z = 2. Electronic spectrum of 1 also reveals a high-spin octahedral environment. Cyclic voltammetry of 1 undergoes one wave of a one-electron transfer corresponding to $Ni^{II}/Ni^{III}$ process. TGA curve for 1 shows three-step weight loss. The electronic spectra, electrochemical and TGA behavior of the complex are significantly affected by the nature of the axial $Hcda^-$ ligand.

• 대한화학회지
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• 제62권1호
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• pp.14-18
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• 2018

The complexes $[Zn(L)(H_2O)_2]{\cdot}2NO_2$ (1) and $[Zn(L)(NO_3)_2]$ (2) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo $[14,4,0^{1.18},0^{7.12}]$docosane) have been synthesized and structurally characterized. The compound 1 crystallizes in the monoclinic system $P2_1/c$ with a = 8.74650(10), b = 18.6880(3), c = $7.96680(10){\AA}$, ${\beta}=109.1920(10)^{\circ}$, $V=1229.84(3){\AA}^3$, Z = 2. The compound 2 crystallizes in the monoclinic system P1 with a = 8.1292(5), b = 8.9244(5), c = $9.1398(5){\AA}$, ${\alpha}=68.035(2)$, ${\beta}=70.109(2)$, ${\gamma}=75.649(3)^{\circ}$, $V=572.70(6){\AA}^3$, Z = 1. The crystal structures of the compounds 1 and 2 show a distorted octahedral coordination geometry around the zinc(II) ion, with four secondary amines and two oxygen atoms of the two water and two nitrate ligands at the axial position. The TGA behaviors of the complexes are significantly affected by the nature of the tetraaza macrocycle and the axial ligands.

• Bulletin of the Korean Chemical Society
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• 제12권2호
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• pp.130-137
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• 1991

The following new cryptand 221 complexes of lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate have been synthesized: $(Ln(C_{16}H_{32}N_2O_5)(H_2O)_2(NO_3)_3\ and \((UO_2)_2(C_{16}H_{32}N_2O_5)(H_2O)_4(NO_3)_4$. These complexes have been identified by elemental analysis, moisture titration, conductivity measurements and various spectroscopic techniques. The proton and carbon-13 NMR as well as calorimetric measurements were used to study the interaction of cryptand 221 with La(Ⅲ), Pr(Ⅲ ), Ho(Ⅲ) and $UO_2(Ⅱ)$ ions in nonaqueous solvents. The bands of metal-oxygen atoms, metal-nitrogen atoms and O-U-O in the IR spectra shift upon complexation to lower frequencies, and the vibrational spectra ({\delta}NMN$) of metal-amide complexes in the crystalline state exhibit lattice vibrations below 300 $cm^{-1}$. The NMR spectra of the lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate complexes in nonaqueous solvents are quite different, indicating that the ligand exists in different conformation, and also the $^1H$ and $^{13}C-NMR$ studies indicated that the nitrogen atom of the ring has greater affinity to metal ions than does the oxygen atom, and the planalities of the ring are lost by complexation with metal ions. Calorimetric measurements show that cryptand 221 forms more stable complexes with $La^{3+}$ and $Pr^{3+}$ ions than with $UO^{22+}$ ion, and $La^{3+}/Pr^{3+}$ and $UO^{22+}/Pr^{3+}$ selectivity depends on the solvents. These changes on the stabilities are dependent on the basicity of the ligand and the size of the metal ions. The absorption band (230-260 nm) of the complex which arises from the direct interaction of macrocyclic donor atoms with the metal ion is due to n-{\delta}*$ transition and also that (640-675 nm) of $UO^{22+}$-cryptand 221 complex, which arises from interaction between two-dioxouranium(Ⅵ) ions in being out of cavity of the ligand ring is due to d-d* transition.

• 환경위생공학
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• 제11권1호
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• pp.17-25
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• 1996

Resins with cryptand 22 macrocyclic ligand attached to chloromethylated styrene-1,4-divinylbenzene by substitution reaction were prepared and the effect of pH, metal concentration and cross-linkage of the matrix on the adsorption for $UO_2^{2+}$, $Cd^{2+}$ and $Sm^{3+}$ was investigated. The metal ion was not adsorbed on the resins pH range below 3 but above pH 4 fast adsorption behavior was showed. The resin selectivity determined in ethanol matrix was in increasing order $UO_2^{2+}{\;}>Cd^{2+}{\;}Sm^{3+}$. In addition, these metal ion could be separated on the column packed with 1% crosslinked resin by pH 2.5 $HNO_3$ as an eluent.

• 분석과학
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• 제15권1호
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• pp.91-95
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• 2002

Carbon paste electrodes, modified with 5,6,14,15-dibenzo-1,4-dioxa-8,12-diazacyclopentadeca-5,14-diene containing different ligating atoms of oxygen and nitrogen, have been employed for the voltammetric determination of Ag(I) ion from aqueous solution. The voltammetric response was characterized with respect to paste composition, preconcentration method, kind of anion, variation of pH, Ag(I) ion concentration, and possible interferences. Linear calibration curves were obtained for Ag(I) ion concentration ranging from $3.0{\times}10^{-6}M$ to $8.0{\times}10^{-5}M$, and detection limit was $8.5{\times}10^{-7}M$.

• 한국결정학회지
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• 제9권2호
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• pp.92-95
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• 1998

The structure of bis(isocyanto-N)nickel (II) complex, [Ni(L)(NCO)2] (L: 2,5,9,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane), is centrosymmetric and the central nickel has an axially elongated octahedral geometry with two nitrogen atoms of the isocyanate ligand.

• 통합자연과학논문집
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• 제7권2호
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• pp.130-137
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• 2014

Resins were synthesized by mixing N-phenylaza-15-crown-5 macrocyclic ligand attached to styrene (2th petroleum in 4th class hazardous materials) divinylbenzene (DVB) copolymer with crosslink of 1%, 2%, 6%, and 12% by substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, thermo gravimetric analysis (TGA), surface area, and IR-spectroscopy. The effects of pH, equilibrium arrival time, dielectric constant of solvent and crosslink on adsorption of metal ions by the synthetic resin adsorbent were investigated. The metal ions were showed fast adsorption on the resins above pH 4. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order uranium (VI) > zinc (II) > europium (III) ions. The uranium ion adsorbed in the order of 1%, 2%, 6%, and 12% crosslink resin and adsorption of resin decreased in proportion to the order of dielectric constant of solvents.

• Bulletin of the Korean Chemical Society
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• 제16권6호
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• pp.518-523
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• 1995

New square planar nickel(Ⅱ) complexes with various 1-alkyl (4a-4c) and 1-hydroxyalkyl (4d-4f) derivatives of the 14-membered pentaaza macrocycle 8-ethyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane have been synthesized by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary amines. The nitro group and/or hydroxyl group of 4a-4f are not directly involved in the coordination. The nickel(Ⅱ) complexes exist in coordinating solvents such as MeCN, Me2SO, and H2O as equilibrium mixtures of the square planar [Ni(L)]2+(L=4a-4f) and octahedral species [Ni(L)S2]2+(S=solvent molecule). Although the ligand field strength and redox potentials of the complexes are not affected by the nature of the substituents, the formation of octahedral species for 4d-4f in MeCN is strongly restricted by the hydroxyl group. Synthesis, characterization, and solution behaviors of the nickel(Ⅱ) complexes are described.