• Title/Summary/Keyword: metal complexes

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d10 Metal Complexes of a Tripodal Amine Ligand

  • Choi, Kyu-Seong;Kang, Dong-hyun;Lee, Ji-Eun;Seo, Joo-beom;Lee, Shim-Sung
    • Bulletin of the Korean Chemical Society
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    • v.27 no.5
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    • pp.747-750
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    • 2006
  • Research on tripodal complexes has grown in recent decades and has been subject of numerous reports.1-11 The reasons for this interest include their relevance to model functions of metalloenzymes1-3 and their potential applications in catalysis.13-17 The ligand system used most in this category has been tren, the tripodal tetraamine N(CH2CH2NH2)3, and its derivatives.4 The bz3tren is a versatile tetradentate ligand, known to form stable complexes not only with transition metals5-11 including Cu2+, Zn2+ and Co2+ but also anion species.12 However, only few results on the d10 metal complexes with bz3tren have been reported by us10 and others.6,7 As a part of on going efforts, we therefore focus our attention to extend other d10 system that includes heavy metal ions.

Synthesis of α-oximinoketones, Precursor of CO2 Reduction Macrocyclic Coenzyme F430 Model Complexes

  • Kim, Gilhoon;Won, Hoshik
    • Journal of the Korean Magnetic Resonance Society
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    • v.21 no.4
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    • pp.139-144
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    • 2017
  • Ni(II) containing coenzyme F430 catalyzes the reduction of $CO_2$ in methanogen. Macrocyclic Ni(II) complexes with N,O shiff bases have been received a great attention since metal ions play an important role in the catalysis of reduction. The reducing power of metal complexes are supposed to be dependent on oxidoreduction state of metal ion and structural properties of macrocyclic ring moiety that can enhance electrochemical properties in catalytic process. Six different ${\alpha}$-oximinoketone compounds, precursor of macrocyclic ligands used in $CO_2$ reduction coenzyme F430 model complexes, were synthesized with yields over 90% and characterized by NMR. The molecular geometries of ${\alpha}$-oximinoketone analogues were fully optimized at Beck's-three-parameter hybrid (B3LYP) method in density functional theory (DFT) method with $6-31+G^*$ basis set using the ab initio program. In order to understand molecular planarity and substitutional effects that may enhance reducing power of metal ion are studied by computing the structure-dependent $^{13}C$-NMR chemical shift and comparing with experimental results.

Synthesis and Application of the Novel Azomethine Metal Complexes for the Organic Electroluminescent Devices

  • Kim, Seong Min;Kim, Jin Sun;Sin, Dong Myeong;Kim, Yeong Gwan;Ha, Yun Gyeong
    • Bulletin of the Korean Chemical Society
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    • v.22 no.7
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    • pp.743-747
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    • 2001
  • New azomethine metal complexes were synthesized systematically and characterized. Beryllium, magnesium, or zinc ions were used as a central metal cation and aromatic azomethines (L1-L4) were employed as a chelating anionic ligand. Emission peaks o f the complexes in both solution and solid states were observed mostly at the region of 400-500 nm in the luminescence spectra, where blue light was emitted. Three of them (BeL1 (Ⅰ), ZnL2 (Ⅱ), and ZnL3 (Ⅲ)) were sublimable and thus were applied to the organic light-emitting devices (OLED) as an emitting layer, respectively. The device including the emitting layer of Ⅰ exhibited white emission with the broad luminescence spectral range. The device with the emitting layer of Ⅱ showed blue luminescence with the maximum emission peak at 460 nm. Their ionization potentials, electron affinities, and electrochemical band gaps were investigated with cyclic voltammetry. The electrochemical gaps of 2.98 for I, 2.70 for Ⅱ, and 2.63 eV for Ⅲ were found to be consistent with their respective optical band gaps of 3.01, 2.95 and 2.61 eV within an experimental error. The structure of OLED manufactured in this study reveals that these complexes can work as electron transporting materials as well.

Synthesis and Characterization of 1-Transition Metal Complex Substituted-2,3,4,5-Tetraphenyl-1-Silacyclopentadienyl Complexes and Generation of Transition Metal Complex-Substituted Silylene

  • Paek Cheolki;Ko Jaejung;Kong Youngkun;Kim, Chang Hwan;Lee Myong Euy
    • Bulletin of the Korean Chemical Society
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    • v.15 no.6
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    • pp.460-465
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    • 1994
  • New silicon-monosubstituted (${\eta}^4$-2,3,4,5-tetraphenyl-l-silacyclopentadiene)transi tion metal complexes are described. (7-Alkyl-7-silanorbornadienyl)MLn(Alkyl=Methyl: MLn=CpRu$(CO)_2$: Alkyl=Methyl: MLn=CpNi(CO): Alkyl=Ethyl: MLn=CpNi(CO)) complexes were prepared from the corresponding silole-transition metal complexes with dimethylacetylenedicarboxylate. Cycloaddition products were obtained with 2,3-dimethyl-1,3-butadiene, 2,3-butanedione, and 1,4-benzoquinone through the ruthenium-substituted silylene. We have determined the crystal structure of (1-methyl-2,3,4,5-tetraphenyl-l-silacyclopentadien yl)cyclopentadienyldicarbonylruthenium by using graphite monochromated Mo-Ka radiation. The compound was crystallized in the monoclinic space group $P2_{1/c}$ with a = 9.838(l), b = 15.972(3), c = 18.327(3) ${\AA}$, and ${\beta}= 94.28(l)^{circ}$. The ruthenium moiety CpRu$(CO)_2$ on silicon is in an axial position.

Studies on Solvent Extraction and Flotation Technique Using Metal-Dithizone Complexes(II). Determination of Trace Elements in Water Samples by Solvent Sublation

  • 김영상;최윤석;최희선
    • Bulletin of the Korean Chemical Society
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    • v.19 no.10
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    • pp.1036-1042
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    • 1998
  • The preconcentration and determination of trace elements in water samples were studied by a solvent sublation utilizing dithizonate complexation. After metal dithizonates were formed, trace amounts of cadmium, cobalt, copper and lead were floated and extracted into small volume of a water-immiscible organic solvent on the surface of sample solution and determined in the solvent directly by GF-AAS. Several experimental conditions as formation condition of metal-dithizonate complexes, pH of solution, amount of dithizone, stirring time, the type and amount of surfactants, N2 bubbling rate and so on were optimized for the complete formation and effective flotation of the complexes. And also four kinds of light solvents were compared each other to extract the floated complexes, effectively. After the pH was adjusted to 4.0 with 5 M HNO3, 8.0 mL of 0.05% acetone solution of dithizone was added to 1.00 L water sample. The dithizonate complexes were flotated and extracted into the upper methyl isobutylketone (MIBK) layer by the addition of 2.0 mL 0.2% ethanolic sodium lauryl sulfate solution and with the aid of small nitrogen gas bubbles. And this solvent sublation method was applied to the analysis of real water samples and good results of more than 85% recoveries were obtained in spiked samples.

Novel Group 9 Metal Complexes Containing an S,S'-Chelating o-Carboranyl Ligand System: Synthesis, Crystal Structures, and Electrochemical Properties of Dinuclear [{(cod)M}2(S,S'-S2C2B10H10)] (cod = 1,5-cyclooctadiene;M = Rh OR Ir)] and Mononclear Cp*CoI[S,S'-S(S=PMe2)C2B10H10] Metal Complexs

  • Lee, Jong-Dae;Kim, Bo-Young;Lee, Chong-Mok;Lee, Young-Joo;Ko, Jae-Jung;Kang, Sang-Ook
    • Bulletin of the Korean Chemical Society
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    • v.25 no.7
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    • pp.1012-1019
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    • 2004
  • The synthesis of novel group 9 metal complexes containing the S,S'-chelate ligands, $Li_2S_2C_2B_{10}H_{10}$ (2a) and $LiS(S=PMe_2)C_2B_{10}H_{10$} (2b), is described. Two new dinuclear complexes of the type $[{(cod)M}_2(S,S'-S_2C_2B_{10}H_{10})]$ (cod = 1,5-cyclooctadiene; M = Rh (3a), or Ir (3b)) were synthesized by the reaction of chloridebridged dimers $[M({\mu}-Cl)(cod)]_2$ with one molar equivalent of the corresponding dilithium dithiolato ligand $Li_2S_2C_2B_{10}H_{10}$ (2a). X-ray crystal structure analysis of 3a revealed a dinuclear structure in which each (cod)Rh unit is attached to a distinct sulfur atom of a 1,2-dithio-o-carboranyl ligand (2a). Additionally, the electrochemical properties of 3a and 3b were investigated by cyclic voltammetry. In an analogous manner, reaction of the lithium dithiolato ligand $LiS(S=PMe_2)C_2B_{10}H_{10}$ (2b) with $Cp^{\ast}CoI_2(CO)$ produced a mononuclear dithiolato complex, $[Cp^{\ast}CoI{(S,S'-S(S=PMe_2)C_2B_{10}H_{10})}]$ (4), which was characterized by single-crystal X-ray analysis.

Design of Home or Hetero Polynuclear Metal Dendritic Molecule for PDD or PDT

  • Choi, Chang-Shik
    • Proceedings of the Korean Institute of Information and Commucation Sciences Conference
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    • 2021.10a
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    • pp.646-648
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    • 2021
  • The syntheses and properties of polynuclear metal complexes have been reported to develop the easy syntheses and noble photo-characteristics of those complexes for photodynamic diagnosis (PDD) or photodynamic therapy (PDT). We have been focused on the design and synthesis of polynuclear lanthanide dendritic molecule due to long life time of fluorescence. Therefore, we will be presented on the design of home (Eu or Gd) or hetero (Tb or Lu) polynuclear lanthanide dendritic molecule.

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Synthesis, characterization, and biological significance of mixed ligand Schiff base and alizarin dye-metal complexes

  • Laith Jumaah Al-Gburi;Taghreed H. Al-Noor
    • Analytical Science and Technology
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    • v.37 no.4
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    • pp.239-250
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    • 2024
  • This study reports the synthesis of a bi-dentate Schiff base ligand (L), 7-(2-((2-formylbenzylidene) amino)-2-phenylacetamido)-3-methyl-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid, prepared from phthalaldehyde and cephalexin antibiotic. The synthesized Schiff base ligand (L) and the secondary ligand alizarin (Az) are used to prepare the new complexes [M(Az)2(L)] and [Cr(Az)2(L)]Cl, where M = Mn(II), Co(II), Ni(II), Cu(II), and Zn(II). The mode of bonding of the Schiff base has been characterized by UV-Visible, FT-IR, Mass, 1H-, and 13C-NMR spectroscopic techniques, and micro elemental analysis (CHNS). The complexes were characterized using UV-Vis, FT-IR, molar conductance, magnetic moment, and thermal analysis (TG/DTG). The molar conductance data revealed that the complexes are non-electrolytes except for [Cr(L)(Az)2]Cl, which is an electrolytic type 1:1. The Schiff base and its complexes have been tested for their biological activity against two strains of bacteria and one fungus. When screened against gram-positive and gram-negative pathogens, the Az and L ligands and their complexes showed potential antimicrobial activity.

Effects of free metal ions and organo-metal complexes on the absorption of lead and cadmium by plants (식물에 의한 납, 카드뮴 흡수 기작에 미치는 자유이온 및 유기산-중금속 복합체의 영향)

  • Lee, Mina;Seo, Byounghwan;Kim, Kwon-Rae
    • Journal of Applied Biological Chemistry
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    • v.64 no.2
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    • pp.159-164
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    • 2021
  • Heavy metals exist in soils in various chemical forms including free metal ions and organo-metal complexes. The ratio of free metal ions has been known to be highly associated with the plant absorption of heavy metals. This study aims to understand the effect of free ions and organo-metal complexes on the absorption of lead (Pb) and cadmium (Cd) by plants. For this, lettuce grown in a hydroponic system for 28 days was consequently grown another 48 hours using Pb and Cd solutions. The ratios of free ion to organo-metal complexes in the solutions were adjusted at 100:0, 90:10, 70:30, 60:40 by four different organic acids (citric, oxalic, acetic, and humic acid). After that, the concentration of Pb and Cd in lettuce were analyzed. The Pb and Cd absorption by lettuce was more relied on the types of organic acids treated and the type of metals rather than the ratio of free metal ions. For example, citric acid increased the Pb absorption while it decreased the Cd absorption by lettuce. There was no significant relationship between free metal ion ratios and both Pb and Cd uptake by lettuce. It could be explained that citric acid, a relatively higher molecular weight organic acid, has higher ion binding capacity, so it forms organo-Pb complex easily due to the higher affinity of Pb on the binding site in comparison with Cd. Consequently, this complexation would assist Pb uptake by lettuce.

Synthesis and Characterization of Tetradentate N2O2 Schiff Base Ligand and its Rare Earth Metal Complexes (사배위 N2O2 Schiff 염기 리간드와 그 희토류 금속착물의 합성 및 특성)

  • Shelke, Vinod A.;Jadhav, Sarika M.;Shankarwar, Sunil G.;Munde, chut S.;Chondhekar, Trimbak K.
    • Journal of the Korean Chemical Society
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    • v.55 no.3
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    • pp.436-443
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    • 2011
  • The solid complexes of La(III), Ce(III), Pr(III), Nd(III), Sm(III) and Gd(III) with 4-hydroxy-3-(1-{2-(2,4-dihydroxy-benzylidene)-amino phenylimino}-ethyl)-6-methyl-pyran-2-one ($H_2$L) derived from o-phenylenediamine, 3-acetyl-6-methyl-(2H)pyran,2,4(3H)-dione (dehydroacetic acid or DHA) and 2, 4-dihydroxy benzaldehyde have been synthesized and characterized by elemental analysis, conductometry, magnetic susceptibility, UV-visible, FT-IR, $^1H$-NMR, X-ray diffraction, thermal analysis study, and screened for antimicrobial activity. The FT-IR spectral data suggest that the ligand behaves as a dibasic tetradentate ligand with ONNO donor atoms sequence towards central metal ion. From the microanalytical data, the stoichiometry of the complexes has been found to be 1:1 (metal: ligand). The physico-chemical data suggests distorted octahedral geometry for La(III), Ce(III), Pr(III), Nd(III), Sm(III) and Gd(III) complexes. The X-ray diffraction data suggests monoclinic crystal system for La(III) and Ce(III) and orthorombic crystal system for Pr(III) and Nd(III) complexes. Thermal behavior (TG/DTA) of the complexes was studied and kinetic parameters were determined by Horowitz-Metzger and Coats-Redfern methods. The ligand and its metal complexes were screened for antibacterial activity against Staphylococcus aureus, Escherichia coli, Bacillus Sp. and fungicidal activity against Aspergillus Niger, Trichoderma and Fusarium oxysporum.