• Bulletin of the Korean Chemical Society
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• 제11권3호
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• pp.235-238
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• 1990

Complexes of the type[Co(T)(L-pro)], where T is the quadridentate $N_2O_2$-type ligand, N,N'-dimethylethylenediamine-N,N'-diacetate or N,N'-dimethylethylenediamine-N,N'-di-$\alpha$-butyrate, have been prepared. The complexes were separated into the two stereoisomers, $\Delta$-s-cis-[Co(T)(L-pro)] and $\Lambda$-s-cis-[Co(T)(L-pro)]. They were characterized by their proton magnetic resonance, absorption and circular dichroism spectra, elemental analyses.

• 한국환경과학회지
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• 제19권7호
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• pp.849-860
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• 2010

A new $N_3O_2$ pentadentate ligand, N,N'-Bis(2-hydroxybenzyl)-ethylenetriamine(H-BHET 3HCl) was synthesized. The hydrochloric acid salts of Br-BHET 3HCl, Cl-BHET 3HCl, $CH_3O$-BHET 3HCl and $CH_3$-BHET 3HCl containing Br-, Cl-, H-, $CH_3O-$ and $CH_3-$ groups at the para-site of the phenol group of the H-BHEP were synthesized. The structures of the ligands were confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible and mass spectra. The calculated stepwise protonation constants(${\logK_n}^H$) of the synthesized $N_3O_2$ ligands showed six steps of the proton dissociation. The orders of the overall protonation constants($\log{\beta}_p$) of the ligands were Br-BHET < Cl-BHET < H-BHET < $CH_3O$-BHET < $CH_3$-BHET. The orders agreed well with that of para Hammett substituent constants(${\delta}_p$). The calculated stability constants($\logK_{ML}$) between the ligands and heavy metal ions (Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II)) agreed well with the order of the overall proton dissociation constants of the ligands but they showed a reverse order in para Hammestt substituent constants(${\delta}_p$). The order of the stability constants between the heavy metal ions with the synthesized ligands were Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II).

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2351-2357
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• 2011

Three new metal-organic copper(II) complexes, $[Cu(H_2PZTC)_2]_n{\cdot}2nH_2O$ (1), $[Cu(HPZTC){\cdot}2H_2O]_n{\cdot}2nH_2O$ (2), and $Cu_2[(PZHD)(OH)(H_2O)_2]_n$ (3) ($H_3PZTC$ = pyrazine-2,3,5-tricarboxylic acid, $PZHD^{3-}$ = 2-hydroxypyrazine-3,5-dicarboxylate), have been synthesized from $Cu(II)/H_3PZTC$ system under different synthetic conditions, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. In complexes 1 and 2, $H_3PZTC$ ligands loose one and two protons, which were transformed into $H_2PZTC^-$ anion and $HPZTC^{2-}$ dianion under different preparation condition, respectively. Furthermore, two ligands coordinate with Cu(II) cations in different modes, leading to the formation of the different chain structures. In complex 3, $H_3PZTC$ ligand was converted into a new ligand-PZHD by in situ decarboxylation and hydroxylation under a higher pH value than that for complexes 1 and 2. PZHD ligands link the Cu(II) cations to form a 2D layer structure. These results demonstrate that the preparation conditions, including pH value and reaction temperature etc, play an important role in the construction of complexes based on $H_3PZTC$ ligand.

• 대한화학회지
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• 제48권2호
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• pp.215-219
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• 2004

• Bulletin of the Korean Chemical Society
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• 제33권7호
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• pp.2299-2304
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• 2012

Two new metal(II) complexes, $[Mn(dpa)(phen)(H_2O)_2]_n$ (1) ($H_2dpa$ = dephenic acid, phen = 1,10-phenanthroline) and $[Ni_2(nda)(phen)_2(H_2O)_6](nda)(H_2O)$ (2) ($H_2nda$ = 2,6-naphthalenedicarboxylic acid) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. In complex 1, Mn(II) ion is six-coordinated, and Mn(II) ions are bridged by dpa ligands into 1D chains. While, the complex 2 is dimer and two Ni(II) ions are bridged by one nda ligand cooperated with the terminal ligand phen. In each complex, the dicarboxylate ligand is coordinated to metal(II) ions as a bis-monodentate.

• Applied Biological Chemistry
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• 제48권4호
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• pp.326-330
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• 2005

인공 DNase의 새로운 리간드 분자로 설계된 2,9-(N,N-dimethylethylenediamino)-1,10-phenanthroline(A) 및 2,9-(N,N-Dimethylethylenediaminomethyl)-1,10-phenanthroline(B)의 Cu(II) 착 화합물에 의한 2',3'-cAMP의 촉매 가수분해 반응에서 리간드 분자의 아미노기들과 2',3'-cAMP의 인산기 사이에 형성되는 분자내 4개의 수소결합들로 인하여 (A) 및 (B)의 Cu(II) 착 화합물은 2,9-dimethyl-o-phenanthroline의 Cu(II) 착 화합물에 의한 2',3'-cAMP의 촉매 가수분해 반응 속도를 7만배 이상 빠르게 촉진 할 것으로 예측되었다.

• Bulletin of the Korean Chemical Society
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• 제26권10호
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• pp.1501-1502
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• 2005

• 대한화학회지
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• 제32권6호
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• pp.536-542
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• 1988

새로 합성한 N-benzylisonitrosoacetylacetone imine(CH3-CO-CNOH-CNCH2${\phi}$-CH3, 이하 H-IAA-NBz)을 리간드로 하는 Nickel(Ⅱ) 착물을 합성하고, 원소분석, 적외선흡수스펙트럼, 핵자기공명스펙트럼, 전자스펙트럼 및 질량스펙트럼등 분광학적인 자료와 자기모멘트 측정으로부터 구조를 구명하였다. 이 착물은 상온에서 매우 안정하며, cis-형 및 trans-형의 기하이성질체가 존재한다. Nickel 이온과 리간드로 1 : 2로 결합한다. 결합된 두 리간드 중 한쪽 리간드는 isonitroso기의 질소원자와 이민의 질소원자가 Nickel(Ⅱ) 이온과 결합하여 5원고리를, 다른쪽 리간드는 isoniroso기의 산소원자와 이민의 질소원자가 Nickel(Ⅱ)이온과 결합하여 6원고리를 형성하여 4각평면구조를 만들고 있다.

• 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.

• Bulletin of the Korean Chemical Society
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• 제31권11호
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• pp.3173-3179
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• 2010

New complex $[Mn(II)H_{1.5}L]_2[Mn(II)H_3L]_2(ClO_4)_5{\cdot}3H_2O$ (1), where $H_3L$ is tris {2-(4-imidazolyl)methyliminoethyl} amine (imtren), has been prepared by reacting manganese(II) perchlorate hexahydrate with the imtren ligand in methanol. X-ray crystallographic study revealed that the imtren ligand hexadentately binds to Mn(II) ion through the three Schiff-base imine N atoms and three imidazole N atoms with a distorted octahedral geometry, and the apical tertiary amine N atom of the ligand pseudo-coordinates to Mn(II), forming overall a pseudo-seven coordination environment. The hydrogen-bonds between imidazole and imidazolate of $[Mn(II)H_{1.5}L]^{0.5+}$ complex ions are extended to build a 2D puckered network with trigonal voids. $[Mn(II)H_3L]^{2+}$ complex ions constitutes another extended 2D puckered layer without hydrogen bonds. Two layers are wedged each other to constitute overall stack of the crystal. Peroxidase activity of complex 1 was examined by observing the oxidation of 2,2'-azinobis(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS) with hydrogen peroxide in the presence of complex 1. Generation of $ABTS^{+{\cdot}}$ was observed by UV-vis and EPR spectroscopies, indicating that the complex 1, a fully-coordinated mononuclear Mn(II) complex with nitrogen-only ligand, has a heme-independent peroxidase activity.