• Title/Summary/Keyword: transition metal complex

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Fabrication, Optoelectronic and Photocatalytic Properties of Some Composite Oxide Nanostructures

  • Zou, C.W.;Gao, W.
    • Transactions on Electrical and Electronic Materials
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    • v.11 no.1
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    • pp.1-10
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    • 2010
  • This is an overview paper reporting our most recent work on processing and microstructure of nano-structured oxides and their photoluminescence and photo-catalysis properties. Zinc oxide and related transition metal oxides such as vanadium pentoxide and titanium dioxide were produced by a combination of magnetron sputtering, hydrothermal growth and atmosphere controlled heat treatment. Special morphology and microstructure were created including nanorods arrays, core-brushes, nano-lollipops and multilayers with very large surface area. These structures showed special properties such as much enhanced photoluminescence and chemical reactivity. The photo-catalytic properties have also been promoted significantly. It is believed that two factors contributed to the high reactivity: the large surface area and the interaction between different oxides. The transition metal oxides with different band gaps have much enhanced photoluminescence under laser stimulation. Use of these complex oxide structures as electrodes can also improve the energy conversion efficiency of solar cells. The mixed oxide complex may provide a promising way to high-efficiency photo emitting materials and photo-catalysts.

Study on Morphology Control of Polymeric Membrane with Clathrochelate Metal Complex (Clathrochelate계 금속 착물을 이용한 고분자 멤브레인 구조 제어)

  • Kim, Nowon;Jung, Boram
    • Membrane Journal
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    • v.24 no.6
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    • pp.472-483
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    • 2014
  • This study is preparation of microporous membranes by using macrocyclic metal ion complexes and extended cage complexes. It is a more favorable way to existing methods because polymer and metal ion-ligand complex system provides a fine control over the phase transition behavior. Chemical functionalization of the polar surface can be obtained. Metal-templated condensation of cyclohexanedione dioxime, hydroxyphenylboronic acid in the presence of metal salts proceeds cleanly in methanol to furnish the metal clathrochelate complexes. Organic/inorganic hybrid membranes were prepared with polyethersulfone (PES), polyvinylpyrrolidone (PVP), ethyleneglycol butyl ether (BE), metal clathrochelate s and DMF by using nonsolvent induced phase inversion method. The structure of membranes was characterized with scanning electron microscopy (SEM) and microflow permporometer. The addition of Fe(II) clathrochelate complex with p-hydroxyphenyl group leads to changes of membrane morphology such as narrow mean pore size distribution, increase of surface pore density and decrease of the largest pore size.

Enhanced Electrical Properties of Light-emitting Electrochemical Cells Based on PEDOT:PSS incorporated Ruthenium(II) Complex as a Light-emitting layer

  • Gang, Yong-Su;Park, Seong-Hui;Lee, Hye-Hyeon;Jo, Yeong-Ran;Hwang, Jong-Won;Choe, Yeong-Seon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.08a
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    • pp.139-139
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    • 2010
  • Ionic Transition Metal Complex based (iTMC) Light-emitting electrochemical cells (LEECs) have been drawn attention for cheap and easy-to-fabricate light-emitting device. LEEC is one of the promising candidate for next generation display and solid-state lighting applications which can cover the defects of current commercial OLEDs like complicated fabrication process and strong work-function dependent sturucture. We have investigated the performance characteristics of LEECs based on poly (3, 4-ethylenedioxythiophene):poly (styrene sulfonate) (PEDOT:PSS)-incorporated transition metal complex, which is tris(2, 2'-bipyridyl)ruthenium(II) hexafluorophosphate in this study. There are advantages using conductive polymer-incorporated luminous layer to prevent light disturbance and absorbance while light-emitting process between light-emitting layer and transparent electrode like ITO. The devices were fabricated as sandwiched structure and light-emitting layer was deposited approximately 40nm thickness by spin coating and aluminum electrode was deposited using thermal evaporation process under the vacuum condition (10-3Pa). Current density and light intensity were measured using optical spectrometer, and surface morphology changes of the luminous layer were observed using XRD and AFM varying contents of PEDOT:PSS in the Ruthenium(II) complex solution. To observe enhanced ionic conductivity of PEDOT:PSS and luminous layer, space-charge-limited-currents model was introduced and it showed that the performances and stability of LEECs were improved. Main discussions are the followings. First, relationship between film thickness and performance characteristics of device was considered. Secondly, light-emitting behavior when PEDOT:PSS layer on the ITO, as a buffer, was introduced to iTMC LEECs. Finally, electrical properties including carrier mobility, current density-voltage, light intensity-voltage, response time and turn-on voltages were investigated.

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Comparative and Structural Analysis of the Interaction between β-Lactoglobulin type A and B with a New Anticancer Component (2,2'-Bipyridin n-Hexyl Dithiocarbamato Pd(II) Nitrate)

  • Divsalar, A.;Saboury, A.A.;Mansoori-Torshizi, H.;Hemmatinejad, B.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.11
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    • pp.1801-1808
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    • 2006
  • The interaction between whey carrier protein $\beta$-lactoglobulin type A and B (BLG-A and -B) and 2,2'-bipyridin n-hexyl dithiocarbamato Pd(II) nitrate (BPHDC-Pd(II)), a new heavy metal complex designed for anticancer property, was investigated by fluorescence spectroscopy combined with chemometry and circular dichroism (CD) techniques. A strong fluorescence quenching reaction of BPHDC-Pd(II) to BLG-A and -B was observed. Hence, BPHDC-Pd(II) complex can be bound to both BLG-A and -B, and quench the fluorescence spectra of the proteins. The quenching constant was determined using the modified Stern-Volmer equation. The binding parameters were evaluated by fluorescence quenching method. The results of binding study provided evidences presence of two and three sets of binding sites on the BLG-B and -A, respectively, for BPHDC-Pd(II) complex. Using fluorescence spectroscopy and chemometry, the ability of BLG-A and -B to form an intermediate upon interaction with BPHDC-Pd(II) complex was assessed. CD studies displayed that under influence of different concentrations of BPHDC-Pd(II) complex, the regular secondary structure of BLG-B had no significant changes, whereas for BLG-A a transition from $\alpha$-helix to $\beta$-structure was appeared. The results for both of BLG-A and -B displayed that BPHDC-Pd(II) complex can induce a conformational transition from the native form to an intermediate state with a slightly opened conformation, which is detectable with chemometry analyses.

Anodic Growth of Vanadium Oxide Nanostructures (Vanadium Oxide 나노구조 형성)

  • Lee, Hyeon-Gwon;Lee, Gi-Yeong
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2018.06a
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    • pp.68-68
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    • 2018
  • Nanoporous or nanotubular metal oxide can be fabricated by anodization of metal substrate in fluoride contained electrolytes. The approach allows various transition metals such as Zr, Hf, Nb, Ta to form highly ordered oxide nanostructures. These oxide nanostructures have various advantages such as high surface area, fast electron transport rate and slow recombination in semiconductive materials. Recently, vanadium oxide nanostructures have been drawn attentions due to their superior electronic, catalytic and ion insertion properties. However, anodization of vanadium metal to form oxide layers is relatively difficult due to ease formation of highly soluble complex in water contained electrolyte during anodization. Yang et al. reported $[TiF_6]^{2-}$ or $[BF_4]^-$ in electrolyte helps to formation of stable oxide layer [1, 2]. However, the reported approaches are very sensitive in other parameters. In this presentation, we deal with the other important key parameters to form ordered anodic vanadium oxide such as pH, temperatures and applied potential.

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Syntheses of New Nitrogen-Oxygen Multidentate Ligands and Their Stability Constants of Transition Metal(Ⅱ) Ions (새로운 질소-산소계 여러 자리 리간드의 합성 및 전이금속(Ⅱ)이온 착물의 안정도상수)

  • Kim, Sun Deuk;Jang, Ki Ho;Kim, Jun Kwang
    • Journal of the Korean Chemical Society
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    • v.42 no.5
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    • pp.539-548
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    • 1998
  • Multidentate N,O-containing ligands, such as N,N'-bis(2-hydroxybenzyl)-ethylenediamine(BHED), N,N'-bis(2-hydroxybenzyl)-propylenediamine(BHPD), N,N'-bis(2-hydroxybenzyl)-diethylenetriamine(BHDT), N,N'-bis(2-hydroxybenzyl)-triethylenetriamine(BHTT) and N,N'-bis(2-hydroxybenzyl)-tetraethylenepentaamine (BHTP) were synthesized by reduction of the imine group of Bis(salicylidene)-ethylendiamine(BSED), Bis (salicylidene)-propylenediamine(BSPD), Bis(salicylidene)-diethylentriamine(BSDT), Bis(salicylidene)-triethylenetetraamine(BSTT) and Bis(salicylidene)-tetraethylenepentaamine(BSTP). Proton dissociation constants of the ligands and stability constants of transition metal(Ⅱ) ion complexes with BHED, BHPD, BHDT, BHTT, and BHTP were determined by potentiometic titration. The sequence of stability constants $(logK_{ML})$ of complex increases as BHED Zn(Ⅱ) which follows the Irving-Williams series.

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Synthesis of Tridentate Poly-amine Ligands and Determination of Stability Constants of Transition Metal Complexes (세자리 폴리아민리간드의 합성과 양성자 해리상수 및 전이금속과의 착물 안정도상수의 결정)

  • Kim, Sun-Deuk;Kim, Jun-Kwang;Ko, Moon-Soo
    • Analytical Science and Technology
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    • v.15 no.2
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    • pp.135-141
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    • 2002
  • The new tridentate poly-amine ligands, N,N-Bis(2-amino-ethyl)-methyl amine${\cdot}$2HBr (BAMA${\cdot}$2HBr), N,N-Bis(2-amino-ethyl)-ethylamine${\cdot}$2HBr (BAEA${\cdot}$2HBr), N,N-Bis(2-amino-ethyl)-propylamine${\cdot}$2HBr (BAPA${\cdot}$2HBr) and N,N-Bis(2-amino-ethyl)-butylamine${\cdot}$2HBr (BABA${\cdot}$2HBr) were synthesized as their dihydrobromic-salt and characterized by EA, IR, NMR and Mass spectroscopy. The protonation constants of the ligands and stability constants of transition metal(II) complexes were determined in aqueous solutions by potentiometry and compared with diethylenetriamine. Stability constants for transition metal complexes of ligands are in the order of BAMA < BAEA < BAPA > BABA. The larger value of stability constants of BAPA compared to these BABA, may be attributed to the more distorted structure of the complex due to the increased steric crowding caused by the presence of the bulky N-butyl group.

A Series of Transition-metal Coordination Complexes Assembled from 3-Nitrophthalic Acid and Thiabendazole: Synthesis, Structure and Properties

  • Xu, Wen-Jia;Xue, Qi-Jun;Liang, Peng;Zhang, Ling-Yu;Huang, Yan-Feng;Feng, Yu
    • Bulletin of the Korean Chemical Society
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    • v.35 no.1
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    • pp.218-224
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    • 2014
  • In order to explore new coordination frameworks with novel designed 3-nitrophthalic acid and the same N-donor ancillary ligand, a series of novel coordination complexes, namely, $[Cd_2(3-NPA)_2(TBZ)_2(H_2O)_2]{\cdot}2H_2O$(1), $[Zn_2(3-NPA)_2(TBZ)_2]$(2), $[Zn_2O(3-NPA)(TBZ)(H_2O)]_n$(3), $[Co(3-NPA)(TBZ)(H_2O)]_n$(4) (3-$NPAH_2$ = 3-nitrophthalic acid), have been hydrothermally synthesized through the reaction of 3-nitrophthalic acid with divalent transition-metal salts in the presence of N-donor ancillary coligand (TBZ = thiabendazole). As a result of various coordination modes of the versatile 3-$NPAH_2$ and the coligand TBZ, these complexes exhibit structural diversity. X-ray structure analysis reveals that 1 and 2 are 0D molecular rings, while 3 and 4 are one-dimensional (1D) infinite chain polymers. And the weak O-H${\cdots}$O hydrogen bonds and C-H${\cdots}$O nonclassical hydrogen bonds as well as ${\pi}-{\pi}$ stacking also play important roles in affecting the final structure where complexes 1, 3 and 4 have 3D supramolecular architectures, while complex 2 has a 2D supramolecular network. Also, IR spectra, fluorescence properties and thermal decomposition process of complexes 1-4 were investigated.

Alkali-Metal Ion Catalysis and Inhibition in SNAr Reaction of 1-Halo-2,4-dinitrobenzenes with Alkali-Metal Ethoxides in Anhydrous Ethanol

  • Kim, Min-Young;Ha, Gyu Ho;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.35 no.8
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    • pp.2438-2442
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    • 2014
  • A kinetic study is reported for $S_NAr$ reaction of 1-fluoro-2,4-dinitrobenzene (5a) and 1-chloro-2,4-dinitrobenzene (5b) with alkali-metal ethoxides (EtOM, M = Li, Na, K and 18-crown-6-ether complexed K) in anhydrous ethanol. The second-order rate constant increases in the order $k_{EtOLi}$ < $k_{EtO^-}$ < $k_{EtONa}$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for the reaction of 5a and $k_{EtOLi}$ < $k_{EtONa}$ < $k_{EtO^-$ < $k_{EtOK}$ < $k_{EtOK/18C6}$ for that of 5b. This indicates that $M^+$ ion behaves as a catalyst or an inhibitor depending on the size of $M^+$ ion and the nature of the leaving group ($F^-$ vs. $Cl^-$). Substrate 5a is more reactive than 5b, although the $F^-$ in 5a is ca. $10pK_a$ units more basic than the $Cl^-$ in 5b, indicating that the reaction proceeds through a Meisenheimer complex in which expulsion of the leaving group occurs after the rate-determining step (RDS). $M^+$ ion would catalyze the reaction by increasing either the nucleofugality of the leaving group through a four-membered cyclic transition state or the electrophilicity of the reaction center through a ${\pi}$-complex. However, the enhanced nucleofugality would be ineffective for the current reaction, since expulsion of the leaving group occurs after the RDS. Thus, it has been concluded that $M^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through a ${\pi}$-complex between $M^+$ ion and the ${\pi}$-electrons in the benzene ring.

Effect of Ancillary Ligand, Phenyl group, on the Emission Spectrum of Pt(II) Complex Useful for Organic Light-Emitting Device (유기전기발광소자에 사용될 수 있는 백금 착물에 대해 보조리간드 phenyl 기가 발광스펙트럼에 미치는 영향)

  • Lee, Seung-Hee;Lee, Ho-Joon
    • Journal of the Korean Applied Science and Technology
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    • v.25 no.2
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    • pp.265-268
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    • 2008
  • Among the efforts to increase the efficiency of organic light-emitting device (OLED), there is a way: doping phosphorescent materials. As a phosphorescent material, complexes of heavy transition metal, platinum, were synthesized. $Cl^-$ ion and phenyl group were used as ancillary ligands with 2-(2-pyridyl)benzimidazole (pbi) as a chromophore. The complexes were analysed by FAB-mass spectrometer and absorption and emission spectra were obtained. A phenyl group was able to shift the emission band of the complex even if it's not a chromorphore.