• Title/Summary/Keyword: -diketonate

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Synthesis and Characterization of Holmium Complexes Containing $\beta$-Diketonate Ligands

  • 이정해;정영숙;손윤수;강성주
    • Bulletin of the Korean Chemical Society
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    • v.19 no.2
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    • pp.231-235
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    • 1998
  • Two holmium β-diketonate complexes, Ho(hfa)3(H2O)2 (1) and [Ho(hfa)3(H2O)2](triglyme) (2), have been prepared and characterized by IR, TGA, and single-crystal X-ray analyses. These complexes show polymeric chains by the intermolecular hydrogen bondings. The donor atoms of the intermolecular hydrogen bonding in both complexes are hydrogen atoms of the coordinated water molecules. The acceptor atoms in 1 are the carbonyl oxygen atoms of β-diketonate ligands whereas those in 2 are oxygen atoms of the triglyme ligand. While compound 1 decomposes cleanly to Ho2O3, compound 2 sublimes intact. Crystal data for 1 and 2 are as follows: Ho(hfa)3(H2O)2 triclinic P1, a=10.158(4), b=11.628(2), c=12.579(6) Å, α=67.02(3)°, β=73.95(4)°, γ=76.12(2)°, V=1299.8(8) Å3. [Ho(hfa)3(H2O)2](triglyme), monoclinic P21/c, a=12.559(3), b=19.111(2), c=16.789(6) Å, β=110.59(4)°, V=3772(2) Å3.

Photoluminescence analysis of Lewis base coordinate europium(III) β-diketonate complex (유로퓸(III) β-디케토네이트 착물의 루이스 염기 배위에 따른 발광 특성 분석)

  • Sung-Hwan, Lee;Gyu-Hwan, Lee
    • Analytical Science and Technology
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    • v.28 no.3
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    • pp.204-211
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    • 2015
  • Lanthanide complexes have attracted much attention because of their unique light emitting property. The light-emitting efficiencies of europium β-diketonate complexes were compared with those of complexes coordinated by the ligands of amines or phosphine oxides. The results demonstrated that the complexes that were coordinated by phosphine oxides had higher light-conversion performance than those coordinated by amines. The highest light-emitting efficiency was observed when the ligand of trioctylphosphine oxide was coordinated. In order to determine the coordination equivalency of trioctylphosphine oxide in the above complexes, 31P-NMR and their photoluminescence spectra were measured. The findings showed that the europium β-diketonate complex had one or two coordination equivalencies of trioctylphosphine oxide according to the steric hindrance of its original ligand.

Study on the Development of CVD Precursors II-Synthesis and Properties of New Lathanum β-diketonates

  • 임종태;홍성택;이중철;이익모
    • Bulletin of the Korean Chemical Society
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    • v.17 no.11
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    • pp.1023-1031
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    • 1996
  • A new synthetic route for the lanthanum β-diketonate compounds via in-situ formed lanthanum alkyl complexes was developed in the process for the development of suitable MOCVD (metal-organic chemical vapor deposition) precursors of PLT, one of the promising material for the ferroelectric film. A series of lanthanum β-diketonate compounds were successfully synthesized by this method. This new method is found to have some merits; versatile method for almost every β-diketone, β-hydroxyketone, and β-hydroxyaldehyde, short reaction time, easy purification for high purity, moderate to high yield, and easy access to anhydrous compounds. In some cases, anhydrous oligomeric products fail to show the higher volatility. On the other hand, some lanthanum β-diketonates with aromatic groups such as La(1,3-biphenyl-l,3-propandione)3 are found to have favorable properties for a precursor of lanthanum oxide, one of major components of PLT, such as low melting point, and much higher decomposition temperature. A plausible pyrolysis mechanism is proposed by the TGA, where consecutive dissociation of R, CO, CH, C, and O fragments occurs.

Study on the Development of CVD Precursors I-Synthesis and Properties of New Titanium β-Diketonates

  • 홍성택;임종태;이중철;Ming Xue;이익모
    • Bulletin of the Korean Chemical Society
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    • v.17 no.7
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    • pp.637-642
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    • 1996
  • Preparation and properties of potential CVD (Chemical Vapor Deposition) precursors for the TiO2, a major component of the perovskite materials such as PT, PLT, PZT, and PLZT were investigated. Reactions between β-diketones and TiMe3, formed in situ failed to produce stable Ti(β-diketonate)3 complexes but a stable purple solid, characterized as (OTi(BPP)2)2 (BPP=1,3-biphenyl-1,3-propanedione) was obtained when BPP was used. Several new Ti(Oi-Pr)2(β-diketonate)2 complexes with aromatic or ring substituents were synthesized by the substitution reaction of Ti(OiPr)4by β-diketones and characterized with 1H NMR, IR, ICP, and TGA. Solid complexes such as Ti(Oi-Pr)2(BAC)2 (BAC=1.-phenyl-2,4-pentanedione), Ti(Oi-Pr)2(BPP)2, Ti(Oi-Pr)2(1-HAN)2 (1-HAN=2-hydroxy-1-acetonaphthone), Ti(Oi-Pr)2(2-HAN)2 (2-HAN=1-hydroxy-2-acetonaphthone), Ti(Oi-Pr)2(ACCP)2 (ACCP=2-acetylcyclopentanone), and Ti(Oi-Pr)2(HBP)2 (HBP=2-hydroxybenzophenone) were found to be stable toward moisture and air. Ti(Oi-Pr)2(ACCP)2 and Ti(Oi-Pr)2(HBP)2 were proved to have lower melting points and higher decomposition temperatures. However, these complexes are thermally stable and pyrolysis under an inert atmosphere resulted in incomplete decomposition. Ti(Oi-Pr)2(DPM)2 (DPM=dipivaloylmethane) and Ti(Oi-Pr)2(HFAA)2 (HFAA=hexafluoroacetylacetone) were sublimed substantially during the thermal decomposition. Pyrolysis mechanism of these complexes are dependent on type of β-diketone but removal of Oi-Pr ligands occurs before the decomposition of β-diketonate ligands.

Electrochemical Properties of Cu(I)hexafluoroacetylacetonate (Cu(I)hexafluoroacetylacetonate 착화합물들의 전기화학적 성질)

  • Choi, Yong-Kook;Jeong, Byeong-Goo;Shin, Hyun-Kook
    • Journal of the Korean Chemical Society
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    • v.37 no.9
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    • pp.806-812
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    • 1993
  • Complexes of $Cu(I)(hfac)PR_3$(P: phosphine and R: Me, Et and Bu) as Cu(I)(${\beta}$-diketonate) compounds have been synthesized and their electrochemical properties have been investigated using glassy carbon and carbon microelectrode in aprotic solvent. Reduction process of $Cu(I)(hfac)PR_3$ compounds carried out one electron pathway to Cu(0) by cyclic voltammetry in acetonitrile solution. Chronoamperometric curve using carbon microelectrode shows that these complexes are one electron process and diffusion coefficients are $4.5{\sim}6.7{\times}10^{-6}cm^2$/sec.

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Preparation of Novel Magnesium Precursors and MgO Thin Films Growth by Atomic Layer Deposition (ALD)

  • Kim, Hyo-Suk;park, Bo Keun;Kim, Chang Gyoun;Son, Seung Uk;Chung, Taek-Mo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2014.02a
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    • pp.364.2-364.2
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    • 2014
  • Magnesium oxide (MgO) thin films have attracted great scientific and technological interest in recent decades. Because of its distinguished properties such as a wide band gap (7.2 eV), a low dielectric constant (9.8), a low refractive index, an excellent chemical, and thermal stability (melting point=$2900^{\circ}C$), it is widely used as inorganic material in diverse areas such as fire resistant construction materials, optical materials, protective layers in plasma display panels, buffer layers of multilayer electronic/photonic devices, and perovskite ferroelectric thin films. Precursor used in the ALD requires volatility, stability, and low deposition temperature. Precursors using a heteroleptic ligands with different reactivity have advantage of selective reaction of the heteroleptic ligands on substrate during ALD process. In this study, we have synethesized new heteroleptic magnesium precursors ${\beta}$-diketonate and aminoalkoxide which have been widely used for the development of precursor because of the excellent volatility, chelating effects by increasing the coordination number of the metal, and advantages to synthesize a single precursor. A newly-synthesized Mg(II) precursor was adopted for growing MgO thin films using ALD.

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A Study of the Development of CVD Precursors III-Synthesis and Properties of New Lead $\beta$-diketonate Derivatives

  • 임종태;이중철;이완인;이익모
    • Bulletin of the Korean Chemical Society
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    • v.20 no.3
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    • pp.355-361
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    • 1999
  • To improve the volatility and stability of lead complexes, the principle of stabilization by saturating the metal coordination sphere by intramolecular coordination through a β-diketonates with an ethereal group has was tested. Several new lead complexes with alkoxyalkyl-substituted β-diketonates, Pb(R1C(O)CHC(O)(CH2)3OR2)2(Rl=t-Bu, Me, OMe, i-Pr, R2=Me, Et), or carboxylate, Pb(OC(O)(CH2)3OEt)2, were prepared by the reaction between Pb(OAc)2 and corresponding alkoxyalkyl-substituted β-diketonates, and they were found to have a viscous liquid phase. The nature of the head (β-diketonate or carboxylate) or tails and substituents of β-diketonates appeared not to be important for the formation of the liquid phase. It is worth mentioning that Pb(OAc)2, which has limited use due to its low solubility, was successfully adopted as a starting material for the preparation of new lead complexes. Easy hydrolysis, reaction with HCl, and 13C NMR spectra indicated that tail portions were not coordinated to the metal as a copper derivative, Cu(t-BuC(O)CHC(O)(CH2)3OMe)2. All these complexes were not volatile enough for the MOCVD experiments, but a methyl derivative, Pb(MeC(O)CHC(O)(CH2)3OEt)2, showed some sublimation. The methoxy derivative, Pb(MeOC(O)CHC(O)(CH2)3OEt)2, was thermally unstable due to possible equilibrium between species coordinating with a keto oxygen atom and an ethereal atom of a methoxy group, which was confirmed by IR and 13C NMR spectra.