• Bulletin of the Korean Chemical Society
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• 제25권12호
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• pp.1757-1763
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• 2004

A new series of nickel(II), cobalt(II)/(III) and copper(II) complexes of 14, 15 and 16-membered of macrocyclic ligands have been prepared and characterized by elemental analyses, IR, UV-VIS and $^1H-NMR$ spectra, magnetic susceptibilities, conductivities, DTA and ESR measurements. Molar conductances in DMF solution indicate that, the complexes are nonelectrolytes except (9-12) complexes. The electronic spectra show that, all complexes are square planar or distorted octahedral geometry. The ESR spectra of solid complexes (4), (8) and (11) show square planar of axial type symmetry $(d_{x2-y2})$ with considerable covalent bond character. However, complex (12) shows a spectrum of octahedral geometry with $d_{z2}$ ground state. Complex (12) shows exploitation in reducing the amount of electron adducts formed in DNA during irradiation with low radiation products.

• 분석과학
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• 제11권5호
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• pp.341-346
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• 1998

$Cu^{2+}$을 2-피리딘카르복살데히드(PyTC)와 반응시켜 $[Cu(PyTC)H_2O)]SO_4$를 얻었다. 이화합물은 1:1 전해질이며 물과 극성 유기 용매에 아주 잘 녹았다. 이 착물의 원소분석, 전기전도도 및 분광학적 데이터에서 이화합물의 구조는 사각평면임을 제시하였다. PyTC를 이용한 Cu(II)의 정량 가능성에 대하여 연구하였다. 구리(II)의 PyTC용액은 pH 4에서 $2.9{\times}10^{-4}M$까지 Beer의 법칙에 따랐다.

• Bulletin of the Korean Chemical Society
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• 제25권6호
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• pp.796-800
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• 2004

The structure of [Cu(tpen)]$(ClO_4)_2$ (tpen = N,N,N',N'-tetrakis(2-pyridylmethyl)-1,2-ethanediamine) has been identified by X-ray crystallography. The copper(II) ion is surrounded by two amine N atoms and three pyridine N atoms of the ligand, making a distorted trigonal-bipyramid. Among the six potential N donor atoms (two amine N and four pyridine N atoms), only one pyridine N atom remains uncoordinated. We examined structural changes on addition of $Cl^-$ to $[Cu(tpen)]^{2+}$(1). The addition of $Cl^-$ in methanol resulted in the formation of a novel dinuclear copper(II) complex $[Cu_2Cl_2(tpen)](ClO_4)_2{\cdot}H_2O$. The structure of the dinuclear complex was verified by X-ray crystallography. Each copper(II) ion in the dinuclear complex showed a distorted square planar geometry with two pyridine N atoms, one amine N atom and one $Cl^-$ ion.

• Bulletin of the Korean Chemical Society
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• 제29권9호
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• pp.1711-1716
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• 2008

The reaction of copper(II) chloride with phenyl-N-[(pyridine-2-yl)methylene]methaneamide (ppmma) leads to a new $\mu$ -chloro bridged dimeric [Cu(ppmma)$Cl_2$]$_2$ complex, whereas a reaction of copper(II) bromide with ppmma affords a monomeric Cu(ppmma)$Br_2$ complex. Both complexes have been characterized by X-ray crystallography and electronic absorption spectroscopy. The crystal structural analysis of [Cu(ppmma)$Cl_2$]$_2$ shows that the two Cu(II) atoms are bridged by two chloride ligands, forming a dimeric copper(II) complex and the copper ion has a distorted square-pyramidal geometry ($\tau$ = 0.2). The dimer units are held through a strong intermolecular $\pi-\pi$ interactions between the nearest benzyl rings. On the other hand, Cu(ppmma)Br2 displayed a distorted square planar geometry with two types of strong intermolecular π-π interaction. EPR spectrum of [Cu(ppmma)$Cl_2$]$_2$ in frozen glas s at 77 K revealed an equilibrium between the mononuclear and binuclear species. The magnetic susceptibilities data of [Cu(ppmma)$Cl_2$]$_2$ and Cu(ppmma)$Br_2$ follow the Curie-Weiss law. No significant intermolecular magnetic interactions were examined in both complexes, and magnetic exchange interactions are discussed on the basis of the structural features.

• Bulletin of the Korean Chemical Society
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• 제15권7호
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• pp.549-553
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• 1994

The 2-(dimethylaminomethyl)thiophene (dmamt) complexes with copper(II) chloride and bromide were prepared and characterized by optical, EPR, XPS spectroscopies and magnetic susceptibility measurements. The low-energy absorption band above 850 nm and the relatively small EPR hyperfine coupling constant ($A_{//}{\simeq}$125 G) indicate the pseudotetrahedral site symmetry around copper(II) ion both in Cu(dmamt)$Cl_2$ and Cu(dmamt)$Br_2$ complexes. The higher satellite to main peak intensity of Cu $2P_{3/2}$ core electron binding energy in XPS spectra also supports the pseudotetrahedral geometry around the copper(II) ions having $CuNSX_2$ chromophores. The distortion from square-planar to pseudotetrahedral symmetry is likely to arise from the steric hindrance of the bulky dmamt ligand in the complex. Magnetic susceptibility study shows that these compounds follow Curie-Weiss law in the temperature range of 77-300 K with positive Weiss constant exhibiting the ferromagnetic interaction between copper(II) ions in solid state.

• 대한화학회지
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• 제55권4호
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• pp.603-611
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• 2011

Ethoxylacetyl oxime 리간드 [HL, (1) 및 $H_2L^1$, (3)]와 아세트산 구리(II) 일수화물을 반응시켜 팔면체 및 사각평면착물을 각각 얻었다. 이들 착물을 원소분석, IR 및 UV-Vis 스펙트럼, 자기수자율, 전기전도도 및 ESR 스펙트럼으로 조사하였다. DMF에서 이들 착물의 몰전기전도도 측정한 결과 비이온성을 보였다. 실온 및 77 K에서 [$(L)_2Cu(H_2O)_2$], (2) 착물의 ESR 스펙트럼은 배위결합성을 갖는 축대칭($d_{x2-y2}$)의 특성을 보이며, 또한 전형적인 쌍극자 상호작용에 의해 큰 띠나비를 갖는다. 그러나 착물 [$(L^1)Cu$], (4)는 고체상태에서 큰 띠넓임으로 인해 초미세 갈라짐이 관찰되지 않았는데, 이는 구리(II) 결합자리들 사이의 스핀-교환 상호작용에 의한 것으로 확인되었다. 실온에서 도포된 구리(II) 착물의 스펙트럼은 배위된 질소원자로 인해 극초미세 갈라짐을 보였다. 또한 이 물질은 공유 결합성을 갖는 축형태($d_{x2-y2}$)의 특성을 보이고, 구리(II) 이온의 환경은 기본적으로 사각-평면 배열을 갖는다. 77 K의 얼어있는 메탄올에서 [$(L_1)Cu$], (4)의 스펙트럼은 이합체 화합물의 삼중항 상태의 특성을 보이며, 두 구리(II) 이온 중심 사이의 거리를 계산한 결과 4.8 이다.

• 대한화학회지
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• 제56권6호
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• pp.679-691
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• 2012

New series of metal complexes of Co(II), Ni(II), Cu(II), Zn(II), Pd(II) and Pt(II) with 4-(p-chlorophenyl)-1-(pyridin-2-yl)thiosemicarbazide (HCPTS) have been synthesized and characterized by elemental analyses, magnetic moment, spectra (IR, UV-Vis, $^1H$ NMR, mass and ESR) and thermal studies. The IR data suggest different coordination modes for HCPTS which behaves as a monobasic bidentate with all metal ions except Cu(II) and Zn(II) which acts as a monobasic tridentate. Based on the electronic and magnetic studies, Co(II), Cu(II), Pd(II) and Pt(II) complexes have square - planner, Ni(II) has mixed stereochemistry (tetrahedral + square planar), while Zn(II) is tetrahedral. Molar conductance in DMF solution indicates the non-ionic nature of the complexes. The ESR spectra of solid copper(II) complex show $g_{\parallel}$ (2.2221) > $g_{\perp}$ (2.0899) > 2.0023 indicating square-planar structure and the presence of the unpaired electron in the $d_x2_{-y}2$ orbital with significant covalent bond character. The thermal stability and degradation kinetics of the ligand and its metal complexes were studied by TGA and DTA and the kinetic parameters were calculated using Coats-Redfern and Horowitz-Metzger methods. The complexes have more antibacterial activity against some bacteria than the free ligand. However, the ligand has high anticancer activities against HCT116 (human colon carcinoma cell line) and HEPG2 (human liver hepatocellular carcinoma cell line) compared with its complexes.

• 대한화학회지
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• 제55권2호
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• pp.199-203
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• 2011

일차원 수소결합형 배위고분자 $[Cu^{II}(C_{13}H_{17}N_3OBr)(C_8H_5O_4)]{\cdot}2H_2O.CH_3OH$을 합성하여 단결정 X-선 회절 연구로 특성을 규명하였다. 단량체 단위는 사각평면의 중심 $Cu^{II}$를 갖고 있다. 네개의 배위자리 중 세자리는 $N_2O$-주개 세트를 갖는 Schiff 염기형 리간드 (4-bromo-2-[(2-piperazin-1-yl-ethylimino)-methyl]-phenol)가 차지하고, 네 번째 자리는 옆에 있는 테레프탈레이트 단위의 산소 원자가 차지한다. 두개의 인접한 중성분자는 분자간 N-H---O 및 O-H---N 수소결합에 의해 연결되어 이합체 쌍을 형성한다. 각 이합체 쌍은 불연속적인 물 및 메탄올 분자에 의해 수소결합으로 다시 연결되어 일차원 초분자 네트워크를 형성한다.

• Bulletin of the Korean Chemical Society
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• 제33권8호
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• pp.2517-2522
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• 2012

New polynuclear poly(hexaaza macrocyclic) copper(II) complexes $[1](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, $[2](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$, and $[3](ClO_4)_{2n}{\cdot}(H_2O)_{2n}$ have been prepared by the one-pot reaction of formaldehyde with ethylenediamine and 1,2-bis(2-aminoethoxy)ethane, 1,3-diaminopropane, or 1,6-diaminohexane in the presence of the metal ion. The polymer complexes contain fully saturated 14-membered hexaaza macrocyclic units (1,3,6,8,10,13-hexaazacyclotetradecane) that are linked by $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-N$, $N-(CH_2)_3-N$, or $N-(CH_2)_6-N$ chains. The mononuclear complex $[Cu(H_2L^5)](ClO_4)_4$ ($H_2L^5$ = a protonated form of $L^5$) bearing two $N-(CH_2)_2-O-(CH_2)_2-O-(CH_2)_2-NH_2$ pendant arms has also been prepared by the metal-directed reaction of ethylenediamine, 1,2-bis(2-aminoethoxy)ethane, and formaldehyde. The polymer complexes were characterized employing elemental analyses, FT-IR and electronic absorption spectra, molar conductance, X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron micrograph (SEM). Electronic absorption spectra of the complexes show that each macrocyclic unit of them has square-planar coordination geometry with a 5-6-5-6 chelate ring sequence. The polymer complexes as well as $[Cu(H_2L^5)]^{4+}$ are quite stable even in concentrated $HClO_4$ solutions. Synthesis and characterization of the polynuclear and mononuclear copper(II) complexes are reported.

• 대한화학회지
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• 제33권5호
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• pp.510-515
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• 1989

테트라에틸렌펜타아민과 포름알데히드의 주형축합반응으로부터 새로운 펜타아자 거대두고리 리간드인 1,3,6,9,12-펜타아자비시클로[10,2,1]펜타데칸(D)의 니켈(II) 및 구리(II) 착화합물 $[Ni(D)]^{2+},\;[Cu(d)]6{2+}\;그리고\;[Cu(D)Cl]^+$를 합성하였다. 거대두고리 리간드인 D에는 한 개의 이미다졸리딘 고리가 있다. $[Ni(D)]^{2+}와 [Cu(D)]^{2+}$는 5-5-5-6 킬레이트고리 배열로 된 평면사각형 구조를 이루며, 5-배위 착이온인 $[Cu(D)Cl]^+$의 구조는 그의 전자스펙트럼으로 볼 때 사각피라미드일 것으로 보인다. 이들 니켈(II) 및 구리(II) 착화합물의 합성과 확인 그리고 분광학적인 특성과 화학적인 특성이 논의된다.