• Title/Summary/Keyword: Metal coordination

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Metal Complexes of Ambidentate Ligands (I). Nickel(II) Complexes of Isonitrosobenzoylacetone Imine Derivatives (Ambidentate Ligand의 금속 착물 (제1보). Isonitrosobenzoylacetone Imine 유도체와 니켈(Ⅱ)의 착물)

  • Man Ho Lee;Dae Sub Oh;Kwang Woo Lee
    • Journal of the Korean Chemical Society
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    • v.22 no.1
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    • pp.19-24
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    • 1978
  • Novel nickel(II) complexes of the type Ni(IBA-NH)(IBA-NR), where IBA-NH and IBA-NR (R=H, methyl, ethyl, n-propyl, iso-propyl, n-butyl or benzyl) represent isonitrosobenzoylacetone imine and its N-alkyl derivative respectively, have been prepared. The ir, nmr, and electronic spectra and magnetic moment of the nickel(II) complexes have been studied. It has been determined that the isonitroso group of IBA-NH coordinates to nickel through the oxygen to form 6-membered chelate ring and that of IBA-NR coordinates to nickel through the nitrogen to form 5-membered ring in square-planar Ni(IBA-NH) (IBA-NR). The coordination manner of the ligands is similar to that of isonitrosoacetylacetone imines obtained by Bose, et al.

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Luminescence Studies of N-Methyllutidone, an Unusually High Triplet Energy Sensitizer (N-메틸루티돈의 루미네센스에 관한 연구)

  • Sang Chul Shim;Myung Ho Hyun;Kuy Ho Chae
    • Journal of the Korean Chemical Society
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    • v.22 no.1
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    • pp.45-51
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    • 1978
  • The luminescence of N-methyllutidone is studied in ethanol matrix at $77^{\circ}C$K. No fluorescence is observed but a strong phosphorescence with the quantum yield of 0.1 and the lifetime of 0.2 sec is recorded. An unusually high triplet energy of 85.1 kcal/mole is determined for the compound from the O-O band of phosphorescence. The cis ${\leftrightarrow}$ trans photoisomerization of high triplet energy olefins such as 2-hexene and trans-1,4-dichlorobutene-2 is efficiently sensitized by N-methyllutidone substantiating the high triplet energy of the compound. The negative polarization of O-O band reveals the emitting triplet state to be $({\pi},{\pi}^*)^3$ state. Alkaline metal salts such as lithium chloride enhances the phosphorescence intensity through cation-N-methyllutidone coordination widening the gap between $({\pi},{\pi}^*)^3$and $(n,{\pi}^*)^3$ states.

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Metal Complexes of Ambidentate Ligands (Ⅲ). Palladium (Ⅱ) Complexes of Isonitrosobenzoylacetone Imine Derivatives (Ambidentate 리간드의 금속착물 (제 3보). Isonitrosobenzoylacetone Imine 유도체와 팔라듐(Ⅱ)의 착물)

  • Tae Sub O;Man Ho Lee;Su Han Kim;Jung Hak Park;Hae Woon Lee
    • Journal of the Korean Chemical Society
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    • v.26 no.1
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    • pp.31-35
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    • 1982
  • Novel palladium(II) complexes of the type Pd(IBA-NH)(IBA-NH') and Pd(IBA-NR)2, where IBA-NH and IBA-NR (R: methyl, ethyl, n-propyl, n-butyl, benzyl) represent isonitrosobenzoylacetone imine and its N-alkyl derivatives respectively, have been prepared. The ir, nmr, and electronic spectra of the palladium(Ⅱ) complexes have been studied. It has been determined that the isonitroso group of IBA-NH coordinates to palladium through the oxygen to form 6-membered chelate ring and that of IBA-NH' coordinates to palladium through the nitrogen to form 5-membered ring in square-planar Pd(IBA-NH)(IBA-NH') and it also has been determined that the isonitroso groups of two IBA-NR coordinates to palladium through the nitrogen to form 5-membered rings in square-planar Pd$(IBA-NR)_2$. The coordination manner of the ligands is similar to that of isonitrosoacetylacetone imines obtained by Bose, et $al.^5$.

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Transition Metal Catalysed Oxidation Reactions and Ligand Effects in Aprotic Solvents (전이금속 촉매작용의 산화반응과 리간드 효과)

  • Kim, Sang-Bock
    • Journal of the Korean Chemical Society
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    • v.47 no.6
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    • pp.585-590
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    • 2003
  • Cobalt oxygen carrier complex N,N'-ethylenebis(3-methoxysalycylideneiminato)cobalt(II), Co(3MeOsalen) was prepared at $25{\circ}C$. UV and visible absorption spectra of the complex and hydrazobenzene were studied in non-aqueous solvent methanol in the range of wavelength 200-600 nm. The oxidation of hydrazobenzene by oxygen in non-aqueous solvent is catalysed by Co(3MeOsalen). In the presence of triphenylphosphine($PPh_3$), the rate decreases in methanol. This is presumably attributable to the coordination of $PPh_3$ to the Co(3MeOsalen), resulting in the catallytically inactive compound. The initial rates of the oxidation of hydrazobenzene with the ligand triphenylphosphine were measured by the theoretical values of the rates, Rate=$k_1+k_2K_1[P]/1+K_1[P]+K_1K_2[P]^2$. This fact would be a poorer σ-donor ligand than methanol.

Amorphous Vanadium Titanates as a Negative Electrode for Lithium-ion Batteries

  • Lee, Jeong Beom;Chae, Oh. B.;Chae, Seulki;Ryu, Ji Heon;Oh, Seung M.
    • Journal of Electrochemical Science and Technology
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    • v.7 no.4
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    • pp.306-315
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    • 2016
  • Amorphous vanadium titanates (aVTOs) are examined for use as a negative electrode in lithium-ion batteries. These amorphous mixed oxides are synthesized in nanosized particles (<100 nm) and flocculated to form secondary particles. The $V^{5+}$ ions in aVTO are found to occupy tetrahedral sites, whereas the $Ti^{4+}$ ions show fivefold coordination. Both are uniformly dispersed at the atomic scale in the amorphous oxide matrix, which has abundant structural defects. The first reversible capacity of an aVTO electrode ($295mAhg^{-1}$) is larger than that observed for a physically mixed electrode (1:2 $aV_2O_5$ | $aTiO_2$, $245mAhg^{-1}$). The discrepancy seems to be due to the unique four-coordinated $V^{5+}$ ions in aVTO, which either are more electron-accepting or generate more structural defects that serve as $Li^+$ storage sites. Coin-type Li/aVTO cells show a large irreversible capacity in the first cycle. When they are prepared under nitrogen (aVTO-N), the population of surface hydroxyl groups is greatly reduced. These groups irreversibly produce highly resistive inorganic compounds (LiOH and $Li_2O$), leading to increased irreversible capacity and electrode resistance. As a result, the material prepared under nitrogen shows higher Coulombic efficiency and rate capability.

Application of Bond Valence Method to Estimate the Valence Charge Distributi on in the Metal-to-Oxygen Bonding Spheres in Perovskites

  • Nhat, Hoang Nam;Chau, Dinh Van;Thuong, Dinh Van;Hang, Nguyen Thi
    • International Journal of Internet, Broadcasting and Communication
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    • v.7 no.1
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    • pp.75-92
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    • 2015
  • This paper presents the application of the bond valence method to estimate the valence charge distribution in several perovskite systems: $La_{{\tilde{1}}x}Pb_xMnO_3$ (x=0.1-0.5), $La_{0.6}Sr_{0.{\tilde{4}}x}Ti_xMnO_3$ (x=0.0-0.25) and $La_{{\tilde{1}}x}Sr_xCoO_3$ (x=0.1-0.5); the reviewing of their crystal structures is also incorporated. The results showed the failure of the elastic bonding mechanism in all studied systems and revealed the general deficit of the valence charge in their unit cells. This valence deficit was not associated with the structural defects and was not equally localized in all coordination spheres. As the content of substitution increased, the charge deficit declined systematically from balanced level, signifying the transfer of valence charge from the ${\tilde{B}}O_6$ to ${\tilde{A}}O_{12}$ spheres. This transfer depended on the valence deviation of spheres and the average reached near 2 electron per unit cell. The possible impact of the limitted accuracy of the available structural data on the bond valence results has also been considered.

Synthesis of the Water Dispersible L-Valine Capped ZnS:Mn Nanocrystal and the Crystal Structure of the Precursor Complex: [Zn(Val)2(H2O)]

  • Hwang, Cheong-Soo;Lee, Na-Rae;Kim, Young-Ah;Park, Youn-Bong
    • Bulletin of the Korean Chemical Society
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    • v.27 no.11
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    • pp.1809-1814
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    • 2006
  • The L-Valinate anion coordinating zinc complex, [$Zn(val)_2(H-2O)$], was isolated and structurally characterized by single crystal X-ray crystallography. The crystal possess orthorhombic symmetry with a space group $P2_12_12_1$, Z = 4, and a = 7.4279(2)$\AA$, b = 9.4342(2)$\AA$, c =20.5862(7)$\AA$ respectively. The compound features a penta-coordinate zinc ion in which the two valine anion molecules are directly coordinating the central zinc metal ion via their N (amine) and O (carboxylate) atoms, and an additional coordination to zinc is made by water molecule (solvent) to form a distorted square pyramidal structure. In addition, further synthesis of the valine capped ZnS:Mn nanocrystal from the reaction of [$Zn(val)_2(H-2O)$] precursor with $Na_2S$ and 1.95 weight % of $Mn^{2+}$ dopant is described. Obtained valine capped nanocrystal was water dispersible and was optically characterized by UV-vis and solution PL spectroscopy. The solution PL spectrum for the valine capped ZnS:Mn nanocrystal showed an excitation peak at 280 nm and a very narrow emission peak at 558 nm respectively. The measured and calculated PL efficiency of the nanocrystal in water was 15.8%. The obtained powders were characterized by XRD, HR-TEM, and EDXS analyses. The particle size of the nanocrystal was also measured via a TEM image. The measured average particle size was 3.3 nm.

Synthesis, Characterization, and Crystal Structures of Iron(Ⅱ) and Manganese(II) Complexes with 4,7-bis(2-pyridylmethyl)-1-thia-4,7-diazacyclononane

  • Delong Zhang;Daryle H. Busch;Nathaniel W. Alcock
    • Bulletin of the Korean Chemical Society
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    • v.19 no.9
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    • pp.897-906
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    • 1998
  • A new synthesis has been developed for 1-thia-4,7-diazacyclononane and the complexation behavior of a particular derivative has been explored. The pentadentate ligand 4,7-bis(2-pyridylmethyl)-l-thia-4,7-diazacyclononane ([9]$N_2SPY_2$) and its iron(Ⅱ) and manganese(Ⅱ) complexes were prepared and characterized. Magnetic moments of 5.17 and 5.90 μB respectively, indicate that the iron(Ⅱ) and manganese(Ⅱ) complexes are high spin. Charge transfer transitions (d-π*) occur for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$at 27027, 25000, and 24390 cm-1 for X=$H_2O$, Cl-, and OH-, respectively. In acetonitrile solution, the cyclic voltammogram of the manganese(Ⅱ) complex exhibits a redox couple at 0.92 V vs. NHE while the redox potentials for [Fe(Il)([9]$N_2SPY_2)(X)]^{n+}$ are 0.70, 0.66, and 0.37 V vs. NHE for X=$H_2O$, Cl-, and OH-, respectively. The d-π* charge transfer energy and Fe(Ⅱ)/Fe(Ⅲ) redox potential for [Fe(Ⅱ)([9]$N_2SPY_2)(X)]^{n+}$ increase in the same order: $H_2O>Cl^- >OH^-$. The crystal structures of the iron(Ⅱ) and manganese(Ⅱ) complexes reveal that the metal ions are sixcoordinate, binding to four nitrogen atoms and a sulfur atom from the pentadentate ligand, as well as a chloride anion, with the chloride and sulfur atoms in cis positions. The two metals have similar coordination geometries, which are closer to trigonal prismatic than octahedral. In both iron and manganese complexes, the M-N($sp_3$) trans to Cl- is 0.07 Å longer than the one cis to Cl- , and M-N($sp^2$) trans to S is 0.05 longer than the one cis to S atom.

Trace Metal Distribution and Ecological Risk Assessment in Marine Sediments from the Southeast Coastal Areas of Korea (남동해 연안 퇴적물 내 미량금속 분포 및 생태위해도 평가)

  • Dong-Woon Hwang;Minkyu Choi;Jae-Hyun Lim;In-Seok Lee;Garam Lee;Sujin Na
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.56 no.4
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    • pp.438-448
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    • 2023
  • The concentrations of trace metals and organic matters in marine sediments collected from southeast Korean coastal areas were investigated. The primary purpose of this study was to evaluate the contamination status, spatial distribution and potential ecological risks associated with the physiochemical composition in the studied areas. We found that the concentrations of trace metals in marine sediments were as follows: Fe > Mn > Zn > Cr > Pb > Cu > As > Cd > Hg. According to the sediment quality guidelines (SQGs) of Korea, concentrations of Zn, Cr, Cu and Cd at all sampling sites were below threshold effect levels (TEL). However, concentrations of As, Hg, and Pb (i.e., at the 94-98% of sampling sites), were below the TEL. In addition, concentration factors (CF) in the surveyed area were found to be associated with low ecological risks, whereas As, Hg, and Cu showed moderate to high risk levels in some inner parts of the studied bays. Finally, the pollution load index (PLI) and ecological risk index (ERI) of the elucidated metals were linked to moderate ecological risk, pointing to the possibility of being deleterious to some benthic organisms.

Preparation and Characteristics of Liquid Silicone Rubber Using Polyorganosiloxane Modified with Dimethylacrylamide (디메틸아크릴아마이드 변성 폴리오가노실록산을 이용한 액상 실리콘 고무의 제조와 그 특성)

  • 강두환;이병철
    • Polymer(Korea)
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    • v.28 no.2
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    • pp.143-148
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    • 2004
  • ${\alpha}$,$\omega$-Hydrogen polyorganosiloxane(HPMDMS) prepolymer was prepared from equilibrium polymerization ofoctamethylcyclotetrasiloxane, 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethyl-cyclotetrasiloxane, and 1,1,3,3-tetramethyl disiloxane as an end-blocker in the presence of tetramethylammonium siloxanolate as a catalyst. Polyorganosiloxane modified with dimethylacrylamide(APMDMS) was prepared by hydrosilylation of HPMDMS with dimethylacrylamide in the presence of Pt catalyst, and followed by coordination of metal oxide (APMDMS-MO), such as NiO and FeO, to the amide moieties of the resulting polymer. The chemical structures of HPMDMS and APMDMS were confirmed by FT-IR and $^1$H-NMR analysis. Liquid silicone rubber containing metal oxide composite (LSRMO) was prepared by compounding APMDMS-MO, ${\alpha}$,$\omega$-vinylpolydimethylsiloxane, and a catalyst in a high speed dissolver. The thermal conductivity of LSRMO composite was determined to be 0.29 W/mK, and the volume resistivity exhibited a lower value than that of LSR composite. The mechanical and thermal properties of LSRMO and LSR composite were measured by UTM and TGA.