• Journal of the Korean Chemical Society
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• v.55 no.4
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• pp.594-602
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• 2011

The effect of ${\alpha}$-, ${\beta}$- and ${\gamma}$-picolines on the stereochemistry of the coordination compounds of lanthanide(III) nitrates derived from 4[N-(furfural)amino]antipyrine semicarbazone (FFAAPS) has been studied. The general composition of the present coordination compounds is [Ln(FFAAPS)$(NO_3)_3$Pic] (Ln=La, Pr, Nd, Sm, Gd, Tb, Dy or Ho and Pic=${\alpha}$-, ${\beta}$- or ${\gamma}$-picolines). All these coordination compounds have been characterized by elemental analyses, molecular weight, molar conductance, magnetic susceptibility, infrared and electronic spectra. The infrared studies suggest that the FFAAPS behaves as a neutral tridentate ligand with N, N, O donor while ${\alpha}$-, ${\beta}$- or ${\gamma}$-picoline is coordinated to the lanthanide(III) ions via heterocyclic N-atom. Nitrates are bicovalently bonded in these compounds. From the electronic spectral data, nephelauxetic effect (${\beta}$), covalence factor ($b^{1/2}$), Sinha parameter (${\delta}%$) and the covalence angular overlap parameter (${\eta}$) have been calculated. Thermal stabilities of these complexes have been studied by thermogravimetric analysis. The coordination number of lanthanide(III) ions in the present compound is found to be ten. The antibacterial studies screening of the primary ligand FFAAPS and the complexes showed that the present complexes have moderate antibacterial activities.

• Applied Chemistry for Engineering
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• v.17 no.5
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• pp.483-489
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• 2006

The behavior of rare earth compounds such as $La_{2}O_{3}$, $CeO_{2}$, and $Ca(OH)_{2}$ on the removal of fluoride and heavy metals in the steel wastewater has been investigated. The removal mechanism of fluoride by rare earth elements has been known to be the formation of insoluble compounds between $F^{-}$ and cations such as $La^{3+}$ and $Ce^{4+}$ produced by the dissociation of rare earth compounds (To reduce the running cost of the fluoride wastewater treatment facility, their fluoride removal efficiencies were compared with those of inexpensive rare earth minerals such as natural lanthanide and cerium compound used as a glass polishing agent). All of the rare earth oxides used in this study showed a higher removal efficiency of fluoride than $Ca(OH)_{2}$ in the wastewater. In the case of artificial HF solution, the removal efficiency of fluoride showed in the order: $CeO_{2}$-mineral < $CeO_{2}$ < $Ca(OH)_{2}$ < $La_{2}O_{3}$-mineral < $La_{2}O_{3}$. However, the removal efficiency of fluoride in the wastewater increased in the following order: $Ca(OH)_{2}$ < $CeO_{2}$ mineral < $CeO_{2}$ < $La_{2}O_{3}$ mineral < $La_{2}O_{3}$. All agents showed high efficiencies for the removal of Mn and total Cr in the rare earth compounds. In the case of $Ca(OH)_{2}$, fluoride removal decreased with increasing pH while. However, the rare earth compounds showed a higher fluoride removal in higher pH condition, the optimum pH condition seemed to be around 7 considering both water quality and fluoride removal. Under the pH 7 condition, the $Ca(OH)_{2}$ was superior to rare earth compounds in Mn removal and the lanthanide was superior to others in total Cr removal.

• Journal of the Korean Chemical Society
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• v.48 no.6
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• pp.577-582
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• 2004

The azacrown compounds, 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, $N-ac_3[15]aneN_3O_2(II_a)$ and 1,4-dioxa-7,10,13-triazacyclopentadecane-N,N',N''-tripropioc acid, $N-pr_3[15]aneN_3O_2(II_b)$ were synthesized by modified methods. Potentiometry was used to determine the protonation constant of the $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$. The stability constants of complexes of the trivalent metal ions of $Ce^{3+},\;Eu^{3+},Gd^{3+},and\;Yb^{3+}$ and divalent metal ions of $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ with the ligands $N-ac_3[15]aneN_3O_2\;and\;N-pr_3[15]aneN_3O_2$ have been determined at $25{\pm}0.1^{\circ}C$ in 0.1 M $NaClO_4$ solution by potentiometric methods. The metal ion affinities of the two triazamacrocyclic ligands with three pendant acetate or propionate groups are compared to those obtained for the similar ligands, 1,7-dioxa-4,10,13-triazacyclopentadecane-N,N',N''-triacetic acid, and 1,7-dioxa-4,10,13- triazacyclopentadecane-N,N',N''-tripropioc acid. The trends in stability of complexes for different metal ions due to changes in the nitrogen position of the donor atoms of the ligand are discussed.

• Journal of the Korean Chemical Society
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• v.36 no.6
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• pp.840-848
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• 1992

An ionizable macrocyclic ligand, diaza-18-crown-6-diisopropionic acid(K22DAP) has been synthesized. Protonation constants of this compound and stability constants with some lanthanides were determined by potentiometric titration method. The protonation constants are log$K_1$ = 9.05, log$K_2$ = 8.37, log$K_3$ = 1.88 and log$K_4$ = 0.99. The logarithmic values of stability constants with La(III), Nd(III), Gd(III) and Lu(III) are 11.14, 11.43, 11.74 and 10.88 respectively. Extraction behavior of Ln(III) ion was investigated using TTA(thenoyltrifluoroacetone) as extractant in the presence of K22DAP as macrocyclic ionophore. It was observed that Ln(K22DAP)TTA is the dominating species in aqueous complexes of La(III) and Nd(III).

• Journal of the Korean Chemical Society
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• v.26 no.1
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• pp.24-30
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• 1982

Contact-only (COM) and dipolar-only (DOM) mixtures of the lanthanide shift reagents were prepared based on the Fi and Gi values deduced using individual Ln$(fod)_3$ (Ln = Pr, Nd, Eu, and Yb) and 4-picoline. The $F_i$ and $G_i$ values obtained directly by COM 1 and by DOM 1, which were appropriate mixture of Pr$(fod)_3$ and Eu$(fod)_3$, agreed well with those values obtained by experiments using individual Ln$(fod)_3$ shift reagents. Ei and Gi values obtained directly by COM 2 and by DOM 2, which were mixtures of Nd$(fod)_3$ and Yb$(fod)_3$, deviated from the expected values. The error was traced to the behavior of the ytterbium complexes.

• Journal of the Korean Vacuum Society
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• v.5 no.4
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• pp.315-326
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• 1996

The electronic structures of 3d and 4d core-levels of rare-earth atoms in the insulating rare-earth (Sm, Eu, Gd, and Tb) compounds were studied with x-ray photoelectron spectroscopy(XPS). It is shown that the intrinsic satellite structure due to the hybridization disappears for chemically stable-earth trivalent heavy rare-earth insulating compounds as the hybridization between f electrons of rare-earth atoms and p electrons of anion atoms decreases due to the lanthanide contraction. Eu atoms at the surface of the stable insulating trivalent Eu compounds are found to be divalent. The satellite peak of Eu 3d core-level spectra at about 10eV higher binding energy side relative the main peak comes from the multiplet structures of $\underline{3d}4f^6$ configuration. The satellite structure appearing at about 15 eV higher binding energy side relative to the main peak in all insulating rare-earth compounds is due to an energy loss process of creating a plasmon.

• Polymer Science and Technology
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• v.5 no.3
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• pp.236-253
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• 1994

양이온형 $d^0\;Cp_2M(R)(L)^+$ 착물과 무염기 $Cp_2M(R)^+$ 착물은 $Cp_2M(R)_2$화합물로부터 쉽게 합성할 수 있다. 이들 친전자성 착물에서는 여러가지 리간드 교환반응, 삽입반응, ${\beta}$-H 제거반응 및 ${\sigma}$-결합 복분해반응이 일어날 수 있다. 일반적으로 $Cp2M(R)(L)^+$ 착물은 불포화도와 전하가 크기때문에 중성의 $Cp_2M(R)(X)$나 $Cp_2M(R)_2$보다 반응성이 크며 $d^0\;{Cp_2}^*M(R)^+$ (M=제 3족과 란탄계) 착물과 여러가지 반응에서 유사한 거동을 보인다. $Cp_2MX_2$를 기초로하여 합성된 Ziegler-Natta 촉매에 의한 올레핀 중합에서 활성점이 $Cp_2M(R)^+$ 양이온이라는 여러가지 직접적인 증거가 발표되었다. 분리가능한 $Cp_2M(R)(L)^+$ 착물은 올레핀중합에서 높은 활성을 보이며, 유기합성의 관점에서 흥미있는 C-C 재조합반응과 같은 다른 여러가지 반응이 일어날 수 있는 기회를 제공한다.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1999.05a
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• pp.582-588
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• 1999

정보화 사회의 발전과 함께 멀티미디어에 대한 관심이 집중되고 있으며, 점유 공간이 작고 가벼우며 대면적이 가능한 정보 표시 디스플레이에 대한 기술은 고부가가치 산업으로 인식되어 지고 있다. 이러한 정보 표시 디스플레이들 중, 전기 발광 소자 (Electroluminescence Display : ELD), 액정 표시 디스플레이 (Liquid Crystal Display LCD), 플라즈마 디스플레이 (Plasma Display Panel) 등의 대한 연구가 세계적으로 매우 활발하게 진행되고 있다. 본 연구에서는 란탄 계열의 금속 착 화합물인 Tb(ACAC)$_3$(Phen)과 Tb(ACAC)$_3$(Phen-Cl)를 이용해 다비이스를 제작한후 광학적 및 전기적 특성을 조사하였다. 또한 luminous efficiency와 cyclic voltametric 방법을 이용해 에너지 밴드로 두 발광 물질인 Tb(ACAC)$_3$(Phen)과 Tb(ACAC)$_3$(Phen-Cl)을 비교.분석하였다. 본 연구의 디바이스 구조를 보면 anode/hole transporting layer (HTL)/emitting material layer (EML)/electron transporting layer (ETL)/cathode와 같고 ETL를 aluminum-tris- (8-hydroxyquinoline) (Alq$_3$)와 bis(10-hydroxybenzo(h)quinolinato)beryllium (Bebq$_2$)를 사용하였으며 HTL 로 N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD)를 사용하였다.

• Proceedings of the KIEE Conference
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• 2000.07c
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• pp.1705-1707
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• 2000

유기 전기발광 디스플레이 (Electroluminescence Display; ELD)는 저전압 구동, 자기발광, 경량박형, 광시야각, 빠른 응답속도 등의 장점으로 차세대 디스플레이의 후보로서 주목받고 있다. Eu complex는 610 nm 부근에서 예리한 스펙트럼의 대역폭을 가지며 붉은색의 강한 형광을 나타내는 유기화합물로 잘 알려져, 있다. 새로이 합성한 란탄계 금속착물인 $Eu(TTA)_{3}TPPO$를 발광층으로 사용하여 적색 발광의 효율을 높이기 위해 소자를 제작하였고, 이 때 구동 전압은 9 V이고 18 V에서 가장 밝은 38cd/$m^2$의 휘도를 나타내었으며 전류밀도는 20mA/$cm^2$ 이었다. 제작된 소자의 EL 스펙트럼은 615 nm로 PL 스펙트럼과 동일하게 예리한 최대 피크를 나타내었고, 순환 전압전류법을 이용하여 각 유기 물질들의 에너지 준위를 알 수 있었으며, 각각의 소자들의 에너지 밴드 다이어그램을 통하여 전기적 특성을 분석하였다.

• 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.