• Title/Summary/Keyword: Metal coordination

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Two d10 Metal Coordination Polymers Based on 1H-1,2,4-Triazole: Synthesis, Structure and Fluorescence

  • Zhang, Xiu-Cheng;Xu, Ling;Liu, Wen-Guang;Liu, Bing
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1692-1696
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    • 2011
  • The reactions of 1H-1,2,4-triazole (Htr) with $MX_2$ ($ZnCl_2$ for 1; $CdBr_2$ for 2) resulted in two coordination polymers, [Zn(tr)Cl]$_n$ (1) and $[Cd(Htr)_2Br_2]_n$ (2). The structural analyses indicate that 1 and 2 feature a 2D layer and 1D triple chain, respectively. In 1, neighouring Zn atoms are connected by ${\mu}_3-1$ ${\kappa}N$: 2 ${\kappa}N$: $4{\kappa}N-tr^-$ anionic ligand into 6- and 16-membered rings, further grow into a 2D sheet. Cd atoms in 2 are bonded by two ${\mu}_2-Br^-$ bridges and neutral ${\mu}_2$-1 ${\kappa}N$: 2 ${\kappa}N$-Htr to form a 1D triple chain. The fluorescent characterizations of 1, 2 and the free Htr ligand feature simlilar emission peakes at 444, 446 and 423 nm respectively, which can be assigned to intra-ligand ${\pi}-{\pi}^*$ transition of (H)tr. The energy gaps of 5.90 eV for 1, 5.16 eV for 2, and 5.93 eV for Htr suggest that the compounds behave as insulators.

Two-Dimensional Lanthanum-BDC Coordination Polymer:Hydrothermal Synthesis and Structure of [La4(BDC)6(H2O)5](H2O)(BDC=benzene-1,3-dicaboxylate) (2차원 La-BDC 배위 고분자: [La4(BDC)6(H2O)5](H2O)의 수열합성 및 구조(BDC=benzene-1,3-dicaboxylate))

  • Kim, Hye Jin;Min, Dong Won;Heo, Hyun Su;Lee, Soon W.
    • Journal of the Korean Chemical Society
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    • v.45 no.6
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    • pp.507-512
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    • 2001
  • The hydrothermal reaction between lanthanum(Ⅲ) nitrate $(La(NO3)3${\cdot}$6H_2O)$ and benzene-1,3-dicarboxylic acid $(H_2BDC)$ in the presence of 1,2-bis(4-pyridyl)ethane gave a 2-D lanthnum-BDC coordination polymer with an empirical formula of $〔La_4$(BDC)_6(H_2O)_5$〕(H_2O)$ (1). X-ray structure analysis of compound 1 revealed that this polymer contains four distinct La metals. The three La metals are 7-coordinate with three different structures: a capped trigonal prism, a capped octahedron, and a pentagonal bipyramid. The remaining La metal has a 8-coordinate, square antiprismatic structure.

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Effect SCM Capacity Factor of Small and Medium-Sized Supplier on Operational Performance: Focused on Moderating Effect of Demand Uncertainty (중소 공급업체의 SCM역량요인이 운영성과에 미치는 영향: 수요불확실성의 조절효과를 중심으로)

  • Kim, Jung-dae
    • Asia-Pacific Journal of Business Venturing and Entrepreneurship
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    • v.12 no.5
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    • pp.117-126
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    • 2017
  • This study analyzed both the effect small and medium-sized suppliers' SCM capacity on the performance and how the moderating effect of demand uncertainty as an environmental factor affects this relation. The study is based on the data collected from the survey of small and medium-sized suppliers operating in electronics, metal, machinery, automobile, and textile. It analyzed the results of survey targeting suppliers of these areas by using structure equation modeling. According to the analyzed result, the relation capital of small and medium-sized supplier affects the performance, but there is no relation between coordination capability and the performance. In case of the moderating effect of demand uncertainty, while there is a positive moderating effect of demand uncertainty between relation capital and performance, there is no any moderating effect between coordination capability and performance. It turns out that the relation capital keep having a positive effect on the performance even if there is a demand uncertainty.

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Hydrocarbon Composite Membranes with Improved Oxidative Stability for PEMFC (산화안정성 향상을 위한 고분자연료전지용 탄화수소복합막의 제조 및 특성연구)

  • Lee, Hyejin;Choi, Young-Woo;Yang, Tae-Hyun;Bae, Byungchan
    • Journal of the Korean Electrochemical Society
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    • v.17 no.1
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    • pp.44-48
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    • 2014
  • Sulfonated poly(arylene ether sulfone)-cerium composite membranes with improved oxidative stability were prepared for proton exchange membrane fuel cell application. Oxidative stability of the composite membranes changed depending on the amount of incorporated metal. Their water uptake, IEC and proton conductivity were also affected. ICP analysis confirmed trace of cerium ion in the composite membranes and $^1H$-NMR indicated successful coordination of sulfonic acid groups with the metal ions. Increasing amount of the cerium ion resulted in decrease in proton conductivities and water uptake, but enhanced oxidative stabilities. A hydrogen peroxide exposure equipment was used for the test of oxidative stability of the composite membranes, which enabled to mimic fuel cell operating condition compared with conventional Fenton's test.

One-Pot Reaction Involving Two Different Amines and Formaldehyde Leading to the Formation of Poly(Macrocyclic) Cu(II) Complexes

  • Lee, Yun-Taek;Kang, Shin-Geol
    • Bulletin of the Korean Chemical Society
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    • v.33 no.8
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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.

Synthesis and Characterization of New Polyaza Non-macrocyclic and Macrocyclic Nickel(II) Complexes Containing One 1,3-Diazacyclohexane Ring

  • Lee, Yun-Taek;Jang, Bo Woo;Kang, Shin-Geol
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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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.

BST Thin Film Multi-Layer Capacitors

  • Choi, Woo Sung;Kang, Min-Gyu;Ju, Byeong-Kwon;Yoon, Seok-Jin;Kang, Chong-Yun
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.319-319
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    • 2013
  • Even though the fabrication methods of metal oxide based thin film capacitor have been well established such as RF sputtering, Sol-gel, metal organic chemical vapor deposition (MOCVD), ion beam assisted deposition (IBAD) and pulsed laser deposition (PLD), an applicable capacitor of printed circuit board (PCB) has not realized yet by these methods. Barium Strontium Titanate (BST) and other high-k ceramic oxides are important materials used in integrated passive devices, multi-chip modules (MCM), high-density interconnect, and chip-scale packaging. Thin film multi-layer technology is strongly demanded for having high capacitance (120 nF/$mm^2$). In this study, we suggest novel multi-layer thin film capacitor design and fabrication technology utilized by plasma assisted deposition and photolithography processes. Ba0.6Sr0.4TiO3 (BST) was used for the dielectric material since it has high dielectric constant and low dielectric loss. 5-layered BST and Pt thin films with multi-layer sandwich structures were formed on Pt/Ti/$SiO_2$/Si substrate by RF-magnetron sputtering and DC-sputtering. Pt electrodes and BST layers were patterned to reveal internal electrodes by photolithography. SiO2 passivation layer was deposited by plasma-enhanced chemical vapor deposition (PE-CVD). The passivation layer plays an important role to prevent short connection between the electrodes. It was patterned to create holes for the connection between internal electrodes and external electrodes by reactive-ion etching (RIE). External contact pads were formed by Pt electrodes. The microstructure and dielectric characteristics of the capacitors were investigated by scanning electron microscopy (SEM) and impedance analyzer, respectively. In conclusion, the 0402 sized thin film multi-layer capacitors have been demonstrated, which have capacitance of 10 nF. They are expected to be used for decoupling purpose and have been fabricated with high yield.

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Selective Synthesis of a New Macropolycycle Containing One N-CH2-N Linkage and Its Reaction with Cu2+ and Ni2+ Ions in Methanol

  • Kang, Shin-Geol;Kweon, Jae-Keun;Jeong, Gyeong-Rok;Lee, Uk
    • Bulletin of the Korean Chemical Society
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    • v.29 no.10
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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+}.

Two New closo- or nido-Carborane Diphosphine Complexes: Synthesis, Characterization and Crystal Structures

  • Kong, Lingqian;Zhang, Daopeng;Su, Fangfang;Li, Dacheng;Dou, Jianmin
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2249-2252
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    • 2011
  • Two new carborane complexes containing closo- or nido-carborane diphosphine ligands with the formula: complex $[Hg(7,8-(PPh_2)_2-7,8-C_2B_9H_{10})_2]$ $CH_2Cl_2$ (1) and $[Ag_2({\mu}-Cl)_2(1,2-(P^iPr_2)_2-1,2-C_2B_{10}H_{10})_2]$ (2) have been synthesized and characterized by elemental analysis, 1H and 13C NMR spectroscopy and X-ray structure determination. The X-ray structure analyses revealed that the carborane diphosphine ligand was degraded from closo-1,2-$(PPh_2)_2-1,2-C_2B_{10}H_{10}$ to nido-[$7,8-(PPh_2)_2-7,8-C_2B_9H_{10}]^-$ in complex 1, while the closo nature of the starting ligand $1,2-(P^iPr_2)_2-1,2-C_2B_{10}H_{10}$ was retained in complex 2. In either of the two complexes, the carborane diphosphine ligand was coordinated bidentately to the Hg(II) or Ag(I) center through its two phosphorus atoms, therefore forming a five-member cheating ring between the carborane ligand and the metal center. The coordination geometry of the metal atom is distorted tetrahedron formed by $P_4$ unit in complex 1 and $P_2Cl_2$ unit in complex 2, respectively.

Structure analysis, and magnetic study of a new Gd-metal-organic framework single crystal grown by the slow-evaporation method (증발법으로 합성된 신규 가돌리늄 금속-유기골격체의 단결정 구조 분석 및 자성학적 특성 연구)

  • Song, Jeong Hwa
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.32 no.5
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    • pp.199-204
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    • 2022
  • A new three-dimensional Gd-MOF, [Gd(p-XBP4)4(H2O)]·W(CN)8; (1; p-XBP4 = N,N'-p-phenylenedimethylenbis (pyridin-4-one)) has been synthesized by slow-evaporation and its crystal structure was characterized by single-crystal X-ray diffraction (SCXRD) analysis. For each GdIII ion, there are seven coordination sites, which are occupied by six oxygen atoms of six p-XBP4 ligands and one oxygen atom from the water molecule. The [W(CN)8]3- anion exists for charge balance with cationic framework. The GdII ions are interconnected by the p-XBP4 ligand to form the three-dimensional structure. Considering the magnetic property of lanthanide ions, magnetic studies of Gd-MOF were investigated by direct-current (DC) magnetic susceptibilities measurements.