• Bulletin of the Korean Chemical Society
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• 제28권5호
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• pp.855-858
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• 2007

• Bulletin of the Korean Chemical Society
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• 제30권5호
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• pp.1113-1117
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• 2009

The one-dimensional coordination polymers, $[Cu^{II}(L)(NO_3)_2]_n$ (1) and {$[Cu^{II}(L)(NO_3)]{\cdot}2H_2O}_{2n} (2), were synthesized from $Cu(NO_3)_2{\cdot}3H_2O$ and 2-[(pyridin-3-ylmethyl)amino]ethanol (L, PMAE) in methanol by controlling the molar ratio of copper(II) salt. Copper(II) ion in 1 has one pyridine group of PMAE whose an aminoethanol group coordinates adjacent copper(II) ion. As the pyridine group is bonded to neighboring copper(II) ion, 1 becomes a one-dimensional chain. Contrary to 1, the structure of 2 shows that the oxygen atom of ethoxide group is bridged between two copper(II) ions, which forms a dinuclear complex. Additionally, the pyridine group of PMAE included one dinuclear unit is coordinated to the other dimeric one each other, which leads to a one-dimensional polymer. Due to the structural differences, 1 exhibits weak antiferromagnetic interaction, while 2 shows strong antiferromagnetic interaction. Due to direct spin exchange via oxygen of PMAE 2 has a much strong spin coupling than 1.

• Bulletin of the Korean Chemical Society
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• 제29권10호
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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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• 제23권4호
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• pp.563-566
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• 2002

Copper complexes have been directly incorporated into cellulose acetate (CA) and the resulting light blue colored homogeneous films of 5-20 wt.% copper acetate complex concentrations are found to be thermally stable up to 200 $^{\circ}C$. The reaction chem istry of Cu in CA has been investigated by reacting them with small gas molecules such as CO, H2, D2, O2, NO, and olefins in the temperature range of 25-160 $^{\circ}C$, and various Cu-hydride, -carbonyl, -nitrosyl, and olefin species coordinated to Cu sites in CA are characterized by IR and UV/Vis spectroscopic study. The reduction of Cu(II) complexes by reacting with H2 gas at the described conditions results in the formation of Cu2O and copper metal nanoparticles in CA, and their sizes in 30-120 nm range are found to be controlled by adjusting metal complex concentration in CA and/or the reduction reaction conditions. These small copper metal particles show various catalytic reactivity in hydrogenation of olefins and CH3CN; CO oxidation; and NO reduction reactions under relatively mild conditions.

• 한국결정학회지
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• 제9권1호
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• pp.11-14
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• 1998

[Cu(L)](NCS)2 (1) (L:2,5,9,12-Tetramethyl-1,4,8,11-tetraazacyclotetradecane) 착물을 합성하고 구조를 규명하였다. 이 착물은 단순결정, 공간군 P21/a, a=7.622(2)Å, b=17.645(2) Å, c=8.223(3) Å, β=109.99(2)˚, Z=2로 결정화 되었다. 이착물의 구조는 최소자승법으로 정밀화 하였으며, 최종 신뢰도 R(Rw)값은 1535개의 회석반점에 대하여 0.087및 0.158이었다. 이 착물의 결정구조는 Cu-N(이차 아민)의 평균 거리가 2.030(4)Å인 평면 사각구조를 갖는다. 축에 놓여있는 NCS-음이온은 Cu-N 거리가 2,842(7)Å로 결합되어 있지 않았다.

• Bulletin of the Korean Chemical Society
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• 제35권7호
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• pp.2043-2048
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• 2014

Two isomers of a new tetraaza macrotricycle 2,2,4,9,9,11-hexaazamethyl-1,5,8,12-tetraazatricyclo[$10.2.2^{5.8}$]-octadecane ($L^2$) containing additional N-$CH_2CH_2$-N linkages, C-meso-$L^2$ and C-racemic-$L^2$, have been prepared by the reaction of 1-bromo-2-chloroethane with C-meso-$L^1$ or C-racemic-$L^1$ ($L^1$ = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). Both C-meso-$L^2$ and C-racemic-$L^2$ react with copper(II) ion to form $[Cu(C-meso-L^2)]^{2+}$ or $[Cu(C-racemic-L^2)]^{2+}$ in dehydrated ethanol, but do not with nickel(II) ion under similar conditions. Crystal structure of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ shows that the complex has distorted square-pyramidal coordination geometry with an apically coordinated water molecule. Unexpectedly, the Cu-N distances [2.016(3)-2.030(3) ${\AA}$] of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ are longer than those [1.992(3)-2.000(3) ${\AA}$] of [Cu(C-racemic-$L^1$)($H_2O$)]$(ClO_4)_2$. As a result, $[Cu(C-racemic-L^2)(H_2O)]^{2+}$ exhibits weaker ligand field strength than $[Cu(C-racemic-L^1)(H_2O)]^{2+}$. The copper(II) complexes readily react with CN- ion to yield the cyano-bridged dinuclear complex $[Cu_2(C-meso-L^2)_2CN]^{3+}$ or $[Cu_2(C-racemic-L^2)_2CN]^{3+}$. Spectra and chemical properties of $[Cu(C-meso-L^2)]^{2+}$ and $[Cu_2(C-meso-L^2)_2CN]^{3+}$ are not quite different from those of $[Cu(C-racemic-L^2)]^{2+}$ and $[Cu_2(C-racemic-L^2)_2CN]^{3+}$, respectively.

• Bulletin of the Korean Chemical Society
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• 제28권10호
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• pp.1781-1786
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• 2007

Two copper(II) complexes, [CuL3](ClO4)2 bearing one N-CH2CH2CONH2 group as well as one N-CH2CH2CN group and [CuL4](ClO4)2 bearing two N-CH2CH2CONH2 groups, have been prepared by the selective hydrolysis of [CuL2](ClO4)2 (L2 = C-meso-1,8-bis(cyanoethyl)-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). The complex [CuL5](ClO4)2 bearing one N-CH2CH2C(=NH)OCH3 and one N-CH2CH2CN groups has been prepared as the major product from the reaction of [CuL2](ClO4)2 with methanol in the presence of triethylamine. In acidic aqueous solution, the N-CH2CH2C(=NH)OCH3 group of [CuL5](ClO4)2 undergoes hydrolysis to yield [CuL6](ClO4)2 bearing both N-CH2CH2COOCH3 and N-CH2CH2CN groups. The crystal structure of [CuL5](ClO4)2 shows that the complex has a slightly distorted square-pyramidal coordination polyhedron with an apical Cu-N (N-CH2CH2C(=NH)OCH3 group) bond. The apical Cu-N bond distance (2.269(3) A) is ca. 0.06 A longer than the apical Cu-O (N-CH2CH2CONH2 group) bond of [CuL4](ClO4)2. The pendant amide group of [CuL3](ClO4)2 is involved in coordination. The carboxylic ester group of [CuL6](ClO4)2 is also coordinated to the metal ion in various solvents but is removed from the coordination sphere in the solid state.

• Bulletin of the Korean Chemical Society
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• 제32권8호
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• pp.2565-2570
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• 2011

The reaction of bromoacetonitrile with 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[$16.4.1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^{10}$) containing a N-$CH_2$-N linkage produces 17-cyanomethyl-3,14-dimethyl-2,6,13,17-tetraazatetracyclo-[$16.4.1^{2.6}.0^{1.18}.0^{7.12}$]tricosane ($L^{11}$). The mono-N-functionalized macrocyclic complexes $[ML^2]^{2+}$ (M = Ni(II) or Cu(II); $L^2$ = 2-cyanomethyl-5,16-dimethyl-2,6,13,17-tetraazatricyclo[$16.4.0.0^{7.12}$]docosane) can be prepared by the reaction of $L^{11}$ with nickel(II) or copper(II) ion in acetonitrile. The N-$CH_2CN$ group attached to $[ML^2]^{2+}$ readily reacts with water or methanol to yield the corresponding complexes of $HL^3$ bearing one N-$CH_2CONH_2$ pendant arm or $L^4$ bearing one $N-CH_2C(=NH)OCH_3$ group. The $N-CH_2CONH_2$ or $N-CH_2C(=NH)OCH_3$ group of each complex is coordinated to the central metal ion. Both $[NiL^4(H_2O)]^{2+}$ and $[CuL^4]^{2+}$ are quite stable in acidic aqueous solutions, but undergo hydrolysis to yield $[Ni(HL^3)(H_2O)]^{2+}$ or $[Cu(HL^3)]^{2+}$ in basic aqueous solutions. In contrast to $[Cu(HL^3)]^{2+}$, $[Ni(HL^3) (H_2O)]^{2+}$ is readily deprotonated to form $[NiL^3 (H_2O)]^+$ ($L^3$ = a deprotonated form of $HL^3$) in basic aqueous solutions.

• 대한화학회지
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• 제40권5호
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• pp.341-346
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• 1996

$(Cin)Cu(NO_3)_2$으로 변성된 턴소반죽전극을 제작하여 $I^-$이온을 벗김전압전류법을 이용하여 정량하였다. $I^-$이온은 변성제인 $(Cin)Cu(NO_3)_2$착물에 배위된 $NO_3^-$와 이온교환에 의해 변전극에 감응하며, 산화전위는 +0.72 V였다, $I^-$ 이온의 최적분석 조건은 다음과 같다: 농축용액의 조성은 0.1 M $KNO_3$, 농축시간은 10분, 탄소분말에 대한 변성제의 함량은 40%(w/w). 선형주사 양극벗김전압전류법(Linear Sweep Anodic Stripping Voltammetry)에 의한 $I^-$이온의 검출한계는 $1.0{\times}10^{-6}M$이며, $2.0{\times}10^{-5}M$에서 구한 상대표준편차는 ${\pm}5.5%$였다. 여러 음이온에 대하여 방해작용을 검토한 결과 $Cl^-,\;Br^-,\;C_2O_4^{2-},\;ClO_4^-$ 등은 $I^-$이온의 정량에 영향을 주지 않았지만, $SCN^-$ 이온은 $I^-$ 이온의 산화전류를 약 32% 감소시켰다.