• Title/Summary/Keyword: Bidentate

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Synthesis, Characterization, Luminescence and Biological Activity of Two Lanthanide Complexes Involving Mixed Ligands

  • Ma, De-Yun;Guo, Hai-Fu;Qin, Liang;Xu, Jun
    • Bulletin of the Korean Chemical Society
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    • v.34 no.9
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    • pp.2774-2780
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    • 2013
  • Two new isostructural dinuclear complexes, $Ln_2(4-cpa)_6(bpy)_2$ (Ln = Eu (1); Tb (2), 4-cpa = 4-chlorophenylacetate, bpy = 2,2'-bipyridine), have been hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. The lanthanide ions are bridged by two bidentate and two terdentate carboxylate groups to give centrosymmetric dimers with $Ln{\cdots}Ln$ separations of 3.967(2) and 3.956(3) ${\AA}$, respectively. Each metal atom is nine-coordinate and exhibits a distorted tricapped trigonal prismatic geometry. Three-dimensional fluorescence spectra show that both 1 and 2 emit bright red and green luminescence at room temperature, with long lifetimes of up to 0.369 ms (at 614 nm) and 0.432 ms (at 543 nm), respectively. Moreover, poor luminescence efficiency has been noted for complex 2. The 4-Hcpa ligand and complexes 1-2 have been screened for their phytogrowth-inhibitory activities against Brassica napus L. and Echinochloa crusgalli L., and the results are compared with the activity of quizalofop-P-ethyl.

MO Studies on the Electronic Structure and Reactivity of Glycinato, Glycine Ester Ligands (Glycinato 및 Glycine Ester 리간드의 전자구조와 반응성에 관한 분자궤도함수론적 연구)

  • Ja Hong Kim
    • Journal of the Korean Chemical Society
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    • v.24 no.1
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    • pp.15-19
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    • 1980
  • CNDO/2, EHT molecular orbital methods are used to investigate the electronic structure and reactivity of glycinato, glycine ester ligands. The results show that bidentate glycinato has a more stable structure, Gly-I with a $105.9^{\circ}$dihedral angle between ${\Delta}O_4C_3C_2$ and ${\Delta}C_3C_2N_1$ than Gly-Ⅱ. The electron inductive effects in the alkyl group substituted glycine ester ligands can also be derived from the calculation. According to the electron density, qN of ligands on the basis of CNDO/2 MO calculations, it is concluded that the stabilities are in the order of glycinato > Gly-Et-ester > Gly-i-Pr-ester > Gly-Me-ester.

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Synthesis and Solution Properties of La(III)-N-ethylmorpholine Complex

  • Anwar, Zeinab M.;Sung, Yong-Kiel
    • Bulletin of the Korean Chemical Society
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    • v.26 no.4
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    • pp.614-618
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    • 2005
  • The complex of the composition LaL(N$O_3)_3\;(H_2O)_2$ is prepared by the reaction of La($NO_3)_3{\cdot}6H_2O$ with Nethylmorpholine in aqueous medium. The ligand is involved in the complex as a neutral species where the chelation occurs via the oxygen of the ligand moiety and the nitrate groups as bidentate ligand. The chemical structure of the studied complex is confirmed through IR, XRD, and thermal analysis data. The complexation equilibria of La(III) with N-ethylmopholine is studied in aqueous medium at ionic strength I = 0.1 mol${\cdot}dm^{-3}\;KNO_3$ and at 25, 35 and 45 ${^{\circ}C}$, respectively. The thermodynamic parameters $\Delta$G, $\Delta$H and $\Delta$S values were calculated to prove the association with the complex formation. It is clearly observed that the process is accompanied by absorption of heat, i.e. endothermic process, while the entropy does not change greatly attributed to the release of constant number of water molecules during chelate formation.

Delicate Difference in Coordinating Nature between Copper(II) and Nickel(II) Ions. Structural Properties of Copper(II) and Nickel(II) Nitrate Containing 1,2-Bis(dimethyl-3-pyridylsilyl)ethane

  • Kim, Shin-A;Kim, Chi-Won;Noh, Tae-Hwan;Lee, Young-A;Jung, Ok-Sang
    • Bulletin of the Korean Chemical Society
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    • v.31 no.8
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    • pp.2158-2162
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    • 2010
  • Studies on the molecular construction and structures of $M(NO_3)_2$ (M = Cu(II), Ni(II)) complexes with 1,2-bis(dimethyl-3-pyridylsilyl)ethane (L) have been carried out. Formation of each molecular skeleton appears to be primarily associated with a suitable combination of bidentate N-donors of L and coordinating nature of octahedral metal(II) ions: [$Cu(NO_3)_2(L)_2$] yields a 2-dimensional sheet structure consisting of 44-membered $Cu_4L_4$ skeleton whereas $[Ni(L)_2(H_2O)_2](NO_3)_2$ produces an interpenetrated 3-dimensional structure consisting of 66-membered cyclohexanoid ($M_6L_6$) skeleton. The Cu(II) ion prefers nitrate whereas the Ni(II) ion prefers water molecules as the fifth and the sixth ligands.

1D and 2D Cobalt(II) Coordination Polymers, Co(ox)(en): Synthesis, Structures and Magnetic Properties

  • Kang, Jaeun;Lee, Yumi;Kim, Seungjoo;Yun, Hoseop;Do, Junghwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.11
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    • pp.3244-3248
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    • 2014
  • Two ethylenediamine cobalt(II) oxalate complexes Co(ox)(en), 1 and $Co(ox)(en){\cdot}2H_2O$, 2 have been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum, TG analysis, and magnetic measurements. In 1, Co atoms are coordinated by two bis-bidentate oxalate ions in transconfiguration to form Co(ox) chains, which are further bridged by ethylenediamine molecules to produce 2D grid layers, Co(ox)(en). In 2, Co atoms are coordinated by bridging oxalate ions in cis-configuration to form Co(ox) chains, and the additional chelation of ethylenediamine to Co atoms completes 1D zigzag chain, Co(en)(ox). Two lattice water molecules stabilize the chains through hydrogen bonding. Magnetic susceptibility measurements indicate that both complexes exhibit weak antiferromagnetic coupling between cobalt(II) ions with the susceptibility maxima at 23 K for 1 and 20 K for 2, respectively. In 1 and 2, the oxalate ligands afford a much shorter and more effective pathway for the magnetic interaction between cobalt ions compared to the ethylenediamine ligands, so the magnetic behaviors of both complexes could be well described with 1D infinite magnetic chain model.

Crystal Structures and Thermal Properties of Two Binuclear Cd(II) Supramolecular Complexes Based on Quinolinecarboxylate Ligand

  • Hao, Hu-Jun;Yin, Xian-Hong;Lin, Cui-Wu;Wei, Shui-Qiang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3255-3260
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    • 2011
  • Two novel binuclear metal-organic coordination complexes $[Cd_2(L)_2(bpy)_2(H_2O)_2]{\cdot}6H_2O$ (1), $[Cd_2(L)_2(phen)_2-(H_2O)_2]{\cdot}2H_2O$ (2) (where L = 2-methylquinoline-3,4-dicarboxylate dianion, bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline) have been synthesized under hydrothermal conditions and characterized by single crystal Xray diffraction, spectral method (IR), elemental analysis and thermal gravimetric analysis (TGA). Both 1 and 2 consist of two Cd(II) atoms bridged by two monoatomic bridging carboxylate groups from two L ligands, and the second carboxylate group of each L is monodentately coordinated to Cd(II), creating a sevenmembered chelating ring. The coordination at each metal nucleus is completed by a water molecule and a chelating bidentate molecule. The 3D structures of the complexes are stabilized by ${\pi}-{\pi}$ stacking interactions and hydrogen-bonds.

Synthesis and Crystal Structure of the Cadmium(II) Complex with Thiocyanate and 1,2-Diaminocyclohexane Ligands (Thiocyanat 및 1,2-Diaminocyclohexane 리간드로 구성된 카드뮴(II) 착물의 합성 및 결정구조)

  • 김인회;서승욱;김종혁;김진규;서일환
    • Korean Journal of Crystallography
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    • v.12 no.4
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    • pp.207-211
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    • 2001
  • The crystal structure of the title complex, Cd(SCN)₂{CH/sub 6/H/sub 10/(NH₂)₂}₂(1) has been analyzed by X-ray single crystallography. The complex 1 crystallizes in the monoclinic system P2₁/ space group with a=11.842(2), b=7.926(2), c=11.291(2) Å, β=106.73(3)°V=1014.8(4)Ų, Z=2, R₁=0.0518 and ωR₂=0.1315 for 1775 independent reflections. The central Cd(II) atom of this com-plex has a slightly distorted octahedral coordination geometry, with the 1,2-Diaminocyclohexane ligands functioning as an N,N'-bidentate and the thiocyanate ligands bonding through the sulfur atom in a trans arrangement.

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Extended Bifurcated Hydrogen Bonds Network Material of Copper(II) Complexes with 2-Dimethylaminomethyl-3-hydroxypyridine: Structures and Magnetic Properties

  • Kang, Sung-Kwon;Lee, Hong-Woo;Sengottuvelan, Nallathambi;Kim, Young-Inn
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.95-99
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    • 2012
  • Two novel copper(II) complexes, [Cu(dmamhp)$(H_2O)_2(SO_4)]_n$ (1) and [Cu(dmamhp)$(NO_3)_2(H_2O)]{\cdot}H_2O$ (2) [dmamhp = 2-dimethylaminomethyl-3-hydroxypyridine] have been synthesized and structurally characterized by single crystal X-ray diffraction analysis. Compound 1 displays a double one-dimensional chains structure, in which each chain is constituted with the distorted octahedral copper(II) complex bridged through bidentate sulfate ligands resulting in a coordination polymer. The bifurcated hydrogen bonds and $\pi-\pi$ interactions play important roles in the formation of the double chains structure. On the other hand, compound 2 adopts a distorted square pyramidal geometry around copper(II) ion and exists as a discrete monomer. There are intermolecular bifurcated hydrogen bonds and $\pi-\pi$ stacking interactions between the monomeric units. The magnetic properties revealed that the paramagnetic behaviors are dominantly manifested and there are no intermolecular magnetic interactions in both compound 1 and 2.

Synthesis and Crystal Structures of Copper(II) Complexes with Schiff Base Ligands: [Cu2(acpy-mdtc)2(HBA)(ClO4)]·H2O and [Cu2(acpy-phtsc)2(HBA)]·ClO4

  • Koo, Bon Kweon
    • Bulletin of the Korean Chemical Society
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    • v.34 no.11
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    • pp.3233-3238
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    • 2013
  • Two new Cu(II) complexes, $[Cu_2(acpy-mdtc)_2(HBA)(ClO_4)]{\cdot}H_2O$ (1) (acpy-mdtc- = 2-acetylpyridine S-methyldithiocarbamate and $HBA^-$ = benzilic acid anion) and $[Cu_2(acpy-phtsc)_2(HBA)]{\cdot}ClO_4$ (2) (acpy-$phtsc^-$ = 2-acetylpyridine 4-phenyl-3-thiosemicarbazate) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. The X-ray analysis reveals that the structures of 1 and 2 are dinuclear copper(II) complexes bridged by two thiolate sulfur atoms of Schiff base ligand and bidentate bridging $HBA^-$ anion. For 1, each of the two copper atoms has different coordination environments. Cu1 adopts a five-coordinate square-pyramidal with a $N_2OS_2$ donor, while Cu2 exhibits a distorted octahedral geometry in a $N_2O_2S_2$ manner. For 2, two Cu(II) ions all have a five-coordinate square-pyramidal with a $N_2OS_2$ donor. In each complex, the Schiff base ligand is coordinated to copper ions as a tridentate thiol mode.

A Study on the Corrosion Inhibition Effects of Sodium Heptanoate for Carbon Steel in Aqueous Solution

  • Won, D.S.;Kho, Y.T.
    • Corrosion Science and Technology
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    • v.3 no.6
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    • pp.227-232
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    • 2004
  • The carboxylates as a corrosion inhibitor has been studied by many researchers because of its environmental safety and low depletion rate. However, conventional test methods of inhibitor such as weight loss measurements, linear polarization resistance and corrosion potential monitoring etc., evaluate uniform corrosion of metals. These methods are unable to evaluate crevice-related corrosions, which are encountered in most of heat exchanging facilities. In order to choose the optimum corrosion inhibitor, the appropriate test methods are required to evaluate their performances in service environment. From this point of view, polarization technique was used to evaluate the characteristics of sodium heptanoate on corrosion behavior for carbon steel. Especially a thin film crevice sensor technique were applied to simulate the crevice corrosion in this study. From these experiments, we found that oxygen as an oxidizing agent was required to obtain stable passive film on the metal. Presence of oxygen, however, accelerated crevice corrosion. Potential shift by oxygen depletion and weakened inhibitive film inside the crevice were responsible for such accelerated feature. It is shown that film for corrosion inhibition is a mixture of sodium heptanoate and iron (II) heptanoate as reaction product of iron surface and sodium heptanoate. The iron (II) heptanoate which has been synthesized by reaction of heptanoic acid and ferrous chloride in methanol solution forms bidentate complex.