• Bulletin of the Korean Chemical Society
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• 제24권3호
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• pp.269-273
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• 2003

The synthesis and properties of 2,13-bis(3'-pyridylmethyl) $(L^3)$, 2,13-bis(4'-pyridylmethyl) $(L^4)$, and 2,13-bis(phenylmethyl) $(L^5)$ derivatives of 5,16-dimethyl-2,6,13,17-tetraazatrcyclo$[16.4.0.^{1.18}0^{7.12}]$docosane are reported. The 3- or 4-pyridylmethyl groups of $[ML^3](ClO_4)_2\;or\;[ML^4](ClO_4)_2$ (M = Ni(Ⅱ) or Cu(Ⅱ)) are not involved in coordination, and the coordination geometry (square-planar) and ligand field strength of the complexes are quite similar to those of $[ML^5](ClO_4)_2$, bearing two phenylmethyl pendant arms. However, the complex formation reactions of $L^3\;and\;L^4$ are strongly influenced by the pyridyl groups, which can interact with a proton or metal ion outside the macrocyclic ring. The macrocycle $L^5$ exhibits a high copper(Ⅱ) ion selectivity against nickel(Ⅱ) ion; the ligand readily reacts with copper(Ⅱ) ion to form $[CuL^5]^{2+}$ but does not react with hydrated nickel(Ⅱ) ion in methanol solutions. On the other hand, $L^3\;and\;L^4$ form their copper(Ⅱ) and nickel(Ⅱ) complexes under a similar condition, without showing any considerable metal ion selectivity. The ligands $L^3\;and\;L^4$ react with copper(Ⅱ) ion more rapidly than does $L^5$ at pH 6.4. At pH 5.0, however, the reaction rate of the former macrocycles is slower than that of the latter. The effects of the 3- or 4-pyridylmethyl pendant arms on the complex formation reaction of $L^3\;and\;L^4$ are discussed.

• Bulletin of the Korean Chemical Society
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• 제34권7호
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• pp.2125-2130
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• 2013

A new nickel(II) complex $[NiL^1]^{2+}$ ($L^1$ = 1-(2-aminoethyl)-3-(N-{2-aminoethyl}aminomethyl-1,3-diazacyclohexane) containing one 1,3-diazacyclohexane ring has been prepared selectively by the metal-template condensation of formaldehyde with N-(2-aminoethyl)-1,3-propanediamine and ethylenediamine at room temperature. The complex reacts with nitroethane and formaldehyde to yield the pentaaza macrocyclic complex $[NiL^2]^{2+}$ ($L^2$ = 8-methyl-8-nitro-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one C-$NO_2$ pendant arm. The reduction of $[NiL^2]^{2+}$ by using Zn/HCl produces $[NiL^3(H_2O)]^{2+}$ ($L^3$ = 8-amino-8-methyl-1,3,6,10,13-pentaazabicyclo[13.3.1]heptadecane) bearing one coordinated C-$NH_2$ pendant arm that is readily protonated in acid solutions. The hexaaza macrocyclic complex $[NiL^4]^{2+}$ ($L^4$ = 8-phenylmethyl-8-nitro-1,3,6,8,10,13-hexaazabicyclo[13.3.1]heptadecane) bearing one N-$CH_2C_6H_5$ pendant arm has also been prepared by the reaction of $[NiL^1]^{2+}$ with benzylamine and formaldehyde. The nickel(II) complexes of $L^1$, $L^2$, and $L^4$ have square-planar coordination geometry in the solid states and in nitromethane. However, they exist as equilibrium mixtures of the square-planar $[NiL]^{2+}$ (L = $L^1$, $L^2$, or $L^4$) and octahedral $[NiL(S)_2]^{2+}$ species in various coordinating solvents (S); the proportion of the octahedral species $[NiL(S)_2]^{2+}$ is strongly influenced by the ligand structure and the nature of the solvent. Synthesis, spectra, and chemical properties of the nickel(II) complexes of $L^1-L^4$ are described.

• 대한화학회지
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• 제57권3호
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• pp.311-315
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• 2013

The geometry structures of hexa-coordinated [NiLX]X complexes ($X=Cl^-,\;Br^-,\;I^-$) {L = 8,9,18,19-tetrahydro-7H,17H-dibenzo[f,o] [1,5,9,13]dioxadiaza cyclohexadecine-8,18-diol} are optimized by density functional theory (DFT) using B3LYP/LANL2DZ. The calculated geometric parameters are in good agreement with the corresponding experimental values. Calculation results about these complexes show that dipole moment decreases, and the energy levels of HOMOs descend from iodo-complex to chloro-complex. The energy levels of HOMOs descend gently from iodo-complex to chloro-complex, while the energy levels of LUMOs in the present complexes are almost similar; therefore the energy gapes between HOMOs and LUMOs increased from iodo-complex to chloro-complex.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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• pp.2701-2704
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• 2010

This work shows that both L2 and L3 bearing two and four N-$(CH_2)_2OCH_3$ groups, respectively, can be prepared selectively by the reaction of $L^1$ with 1-bromo-2-methoxyethane. The di-N-substituted macrocycle $L^2$ readily forms its copper(II) and nickel(II) complexes. The N-$(CH_2)_2OCH_3$ groups in $[CuL^2]^{2+}$ are coordinated to the metal ion, whereas those in $[NiL^2]^{2+}$ are not involved in coordination. Interestingly, $L^3$ reacts with $Cu^{2+}$ ion to form $[Cu(HL^3)]^{3+}$, in which one tertiary amino group is not involved in coordination.

• Bulletin of the Korean Chemical Society
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• 제13권6호
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• pp.659-662
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• 1992

The pressure-jump relaxation method has been used to determine the rate constants for the formation and dissociation of maganese(Ⅱ), cobalt(Ⅱ), and nickel(Ⅱ) with some dicarboxylates in aqueous solution at zero ionic strength. The carboxylate ligands used are 3-nitrophthalate, 4-nitrophthalate, and phenylmalonate. The activation parameters have alse been obtained from the temperature dependence of the rate constants. A dissociative interchange mechanism with a chelate ring closure step as rate determining is employed to interpret the kinetic data of manganese(Ⅱ) and cobalt(Ⅱ) complexes. The rates of formation of nickel(Ⅱ) complexes are controlled by both the solvent exchange step and the chelate ring closure step.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
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• pp.365.2-365.2
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• 2014

Nickel sulfide (NiS) has been utilized in optoelectronic applications, such as transformation-toughening agent for materials used in semiconductor applications, catalysts, and cathodic materials in rechargeable lithium batteries. Recently, high quality nickel sulfide thin films have been explored using ALD/CVD technique. Suitable precursors are needed to deposit thin films of inorganic materials. However, nickel sulfide precursors available for ALD/CVD process are very limited to nickel complexes with dithiocarbamate and alkanethiolate ligands. Therefore, it is essential to prepare novel nickel sulfide suitable for ALD/CVD precesses. Herein we report on the synthesis and characterization of new nickel sulfide complex with designed aminothiolate ligand. Furthermore thin films of NiS have been prepared on silicon oxide substrates by spin coating nickel precursor 10 wt% in THF. The novel complex has been characterized by means of 1H-NMR, elemental analysis, thermogravimetric analysis (TGA), X-ray Diffraction (XRD) and scanning electron microscope (SEM).

• 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.

• Bulletin of the Korean Chemical Society
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• 제23권8호
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• pp.1062-1066
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• 2002

The complexes [Ni(L)(INT)2]${\cdot}$5H2O (1) and [Cu(L)(H2O)](Cl)(INT)${\cdot}$3H2O (2) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18 ,07.12 ]docosane, INT = isonicotinate) have been prepared and characterized by X-ray crystallography, electronic absorption, and cyclic voltammetry. The crystal structure of 1 reveals an axially elongated octahedral geometry with two axial isonicotinate ligands. The electronic spectra, magnetic moment, and redox potentials of 1 also show a high-spin octahedral geometry. However, 2 shows that the coordination environment around the copper atom is a distorted square-pyramid with an axial water molecule. The spectra and electrochemical behaviors of 2 are also discussed.

• Bulletin of the Korean Chemical Society
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• 제24권3호
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• pp.393-396
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• 2003

• Bulletin of the Korean Chemical Society
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• 제30권12호
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• pp.3101-3104
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• 2009