• Title/Summary/Keyword: Rare Earth metal complexes

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Macrocyclic Complexes of Actinide and Lanthanide Metals (Ⅰ). Formation and Properties of Cation Complexes with Macrocyclic Ligands (악틴 및 란탄족금속의 거대고리 착물 (제 1 보). 거대고리 리간드의 금속착물의 형성과 성질)

  • Jeong, O Jin;Choe, Chil Nam;Yun, Seok Jin;Son, Yeon Su
    • Journal of the Korean Chemical Society
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    • v.34 no.2
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    • pp.143-158
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    • 1990
  • Metal complexes were prepared by reacting uranium (Ⅵ), thorium (Ⅳ) and rare earth metal (Ⅲ) ions including Nd (Ⅲ), Sm (Ⅲ) and Ho (Ⅲ) with macrocyclic ligands including five crown ethers, nine crownands and one cryptand ligands, and subjected to NMR studies in order to examine coordination sites of the ligands and compositions of the complexes formed. Among the marcocyclic ligands, crown ethers and crownand ligands have shown down-field shifts of the methylene protons of the lcigands by forming stable complexes with all the metal ions and the differences of chemical shifts were decreased as increasing of the cavity-size of crown ethers for the same metal ions and decreasing of the atomic number of the rare earth metals for the same ligands. It has been found that crownand 22 gave a stable complex with uranium(Ⅵ) ion by the coordination through both oxygen and nitrogen atoms of the ligand whereas no complex was formed with the rare earth metal(Ⅲ) ions, which on the other hand were found to form stable complexes with cryptand 221. The rest of the crowand ligands have also been found to form stable complexes with uranium(Ⅵ) ion by coordinating through all the oxygen and nitrogen atoms of the ligands whereas no complexes were formed with the rare earth metal(Ⅲ) ions. It has also been shown by 1H-NMR study that uranium(Ⅵ), thorium(Ⅳ) and rare earth metal(Ⅲ) ions formed 1:1 complexes with the macrocyclic ligands except for thorium(Ⅳ) complex of 12C4 in which the mole ratio of metal to ligand is 1:2. More stable metal complexes show larger changes in chemical shifts of the coordinated ligand protons. Finally, the rare earth metal(Ⅲ) complexes of 18C6 have shown ligand exchange reaction with the solvent molecules in acetylacetone solution, which was not observed for the uranium (Ⅵ) complexes.

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Synthesis and Characterization of Novel Rare-earth Oxides Precursors

  • Lee, Euy Jin;Park, Bo Keun;Chung, Taek-Mo;Kim, Chang Gyoun
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.366.1-366.1
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    • 2014
  • The rare-earth oxides M2O3 (M=La, Pr, Gd) are good insulators due to their large band gap (3.9eV for Pr2O3, 5.6eV for Gd2O3), they have high dielectric constants (Gd2O3 K=16, La2O3 K=27, Pr2O3 K=26-30) and, compared to ZrO2 and HfO2, they have higher thermodynamic stability on silicon making them very attractive materials for high-K dielectric applications. Another attractive feature of some rare-earth oxides is their relatively close lattice match to that of silicon, offering the possibility of epitaxial growth and eliminating problems related to grain boundaries in polycrystalline films. Metal-organic chemical vapor deposition (MOCVD) has been preferred to PVD methods because of the possibility of large area deposition, good composition control and excellent conformal step coverage. Herein we report on the synthesis of rare-earth oxide complexes with designed alkoxide and aminoalkoxide ligand. These novel complexes have been characterized by means of FT-IR, elemental analysis, and thermogravimetric analysis (TGA).

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A Complexation Study of Novel Triaza and Hexaaza Macrocycles for the Use of Analytical Reagents

  • Wakita, Hisanobu;Yamaguchi, Toshio;Matsuki, Yuuichi;Kurisaki, Tsutomu
    • Analytical Science and Technology
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    • v.8 no.4
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    • pp.449-456
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    • 1995
  • Novel macrocyclic ligands modified with pendant arms, N, N', N'', N''', N'''', N'''''-hexakis(2-aminoethyl)-1, 4, 7, 10, 13, 16-hexaazacyclootadecane [$L_3$, Fig.1] and 1, 4, 7-tris(3-(o-hydroxyphenyl)propyl)-1, 4, 7-triazacyclononane [$L_4$, Fig.1] have been synthesized, and the protonation of $L_3$ and $L_4$ and stability constants of $L_3$ with bivalent transition metal ions and rare earth metal ions were determined by a potentiometry. The obtained results show that the complex formation of $L_3$ depends on the metal ligand ratios, and the stability of the metal complexes does not depend on the sizes of the metal ions, but on the nature of the metal ions. The structures of the rare earth complexes for $L_4$ were characterized by an X-ray absorption spectrometry(XAFS).

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Occurrence and Petrogenesis of Phoscorite-Carbonatite Complexes in the Kola Alkaline Province, Arctic

  • Lee, Mi-Jung;Lee, Jong-Ik;Kim, Yea-Dong
    • Ocean and Polar Research
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    • v.25 no.1
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    • pp.119-128
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    • 2003
  • Although phoscorites and carbonatites form only a minor proportion of the earth's crustal rocks, these unusual rocks and their intimate relation are of both academic and economic importance. Rare metal (Nb, Zr, Ta) and REEs mineralizations are in close relation with the differentiation of these phoscorite-carbonatite complexes (PCCs). Recent integrated petrological and geochemical data on PCCs in the Kola Alkaline Province, Arctic, indicate that phoscorites and associated carbonatites are differentiated from common 'carbonated silicate patental magma'. Various hypotheses for the genesis of phoscorite-carbonatite complexes have been proposed during the last half-century. A simple magmatic fractionation scheme can not explain the chemical and mineralogical characteristics of phoscorite and conjugate carbonatite. Instead, the hypotheses involving liquid immiscibility and coeval accumulation processes are favored to explain the mineralogical and geochemical characteristics of phoscorite and carbonatite association.

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.

Crystal Growth, Electrical and Optical Properties of Cubic $ZrO_2$(10 mol% $Y_2O_3$) Single Crystals Doped With Rare Earth Metal Oxides(RE=Ce, Pr, Nd, Eu, Er) (희토류 금속 산화물(RE=Ce, Pr, Nd, Eu, Er)을 첨가한 큐빅 $ZrO_2$(10 mol% $Y_2O_3$)단결정의 결정성장, 전기적 성질 및 광학적 성질)

  • 정대식;오근호
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.1 no.1
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    • pp.5-16
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    • 1991
  • It was grown Cubic $ZrO_2(10 mol% Y_2O_3)$ single crystals doped with 1 wt% rare earth metal oxides (RE=Ce, Pr, Nd, Eu, Er) by Skull method. It was investigated electrical properties on (111) plane of grown single crystals by Impedance Spectroscopy. It was potted relation between temperature and electrical conductivities and observed the transition at $약300-400^{\circ}$ It was obtained activation energy on the migration of oxygen vacancy between low temperature (before the transition) and high temperature (after the transition till ${\11}500^{\circ}$) and its difference can be seen the activation energy of the formation of oxygen vacancies by break up defect complexes. It was obtained the activation energy according as add yttria and rare earth metal oxides and discussed ionic conduction mechanism. Grown single crystals showed Ce: orange - red, Pr: golden - yellow, Nd: lilac, Eu: light pink, Er: pink due to dopant effect from the light absorption data in the visible range.

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A Study on the Synthesis, Electronic Structure, and Electrochemical Behavior of Rare Earth Metal(III) Complexes (II) (희토류금속(III) 착물들의 합성과 전자적 구조와 전기화학적 거동에 관한 연구 (II))

  • Chil Nam Choe;Se Bong Kim;Nyon Yong Park
    • Journal of the Korean Chemical Society
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    • v.37 no.10
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    • pp.895-902
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    • 1993
  • The chemical behavior of trivalent lanthanide ($Pr^{3+}\;and\;Dy^{3+}$) and organo ligands (phen' and terpy') complexes was investigated by the use of UV/vis-spectrophotometric, magnetization and electrochemical method. The magnitude of crystal field splitting energy, the pairing energy and spin state was obtained from the spectra of complexes. These complexes were founded to be diamagnetics, delocalization and low spin complexes. The electrochemical behavior of complexes was observed by the use of cyclic voltammetry in aprotic media. These reduction peaks were irreversible two step reduction processes by electron transfer.

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Electrical Characterization of Organic Electroluminescent Devices utilizing Rare Earth Metal Complex (희토류 금속 화합물을 이용한 유기 전기 발광 소자의 전기적 특성)

  • 이한성;이상필;최돈수;김영관;김정수
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 1999.11a
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    • pp.103-106
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    • 1999
  • Organic electroluminescent devices (OELDs) have received a great deal of attention due to their potential application as full-color displays. Europium complexes are known as excellent red light-emitting materials for OELDs since they show intense photoluminescence at around 612 nm with a narrow spectral bandwidth. In this study, a novel curopium complex, Eu(TTA)$_3$(TPPO) was synthcsizcd and its photoluminescent and electroluminescent characteristics were investigated with a device structure of ITO/TPD/Eu(TTA)3(TPPO)/A1q$_{3}$ Al, where sharp emission at the wavelength of 615 nm has been observed. Details on the electrical properties of these structures will be also discussed.

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Different Adsorption Behavior of Rare Earth and Metallic Ion Complexes on Langmuir Monolayers Probed by Sum-Frequency Generation Spectroscopy

  • Sung, Woongmo;Vaknin, David;Kim, Doseok
    • Journal of the Optical Society of Korea
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    • v.17 no.1
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    • pp.10-15
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    • 2013
  • Adsorption behavior of counterions under a Langmuir monolayer was investigated by sum-frequency generation (SFG) spectroscopy. By comparing SFG spectra of arachidic acid (AA) Langmuir monolayer/water interface with and without added salt, it was found that the simple trivalent cation $La^{3+}$ adsorbed on AA monolayer only when the carboxylic headgroups are charged (deprotonated), implying that counterion adsorption is induced by Coulomb interaction. On the other hand, metal hydroxide complex $Fe(OH)_3$ adsorbed even on a charge-neutral AA monolayer, indicating that the adsorption of iron hydroxide is due to chemical interaction such as covalent or hydrogen bonding to the headgroup of the molecules at the monolayer.