• Title/Summary/Keyword: 6H_2O$

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The Photovoltaic Effect of Iodine-Doped Metal Free Phthalocyanine/ZnO System (Ⅱ). The Photovoltaic Effect of $ZnO/H_2Pc(I)_x$ Dispersed in Poly(9-vinylcarbazole) (요오드가 도핑된 무금속 프탈로시아닌/산화아연계의 광기전력 효과 (Ⅱ). Poly(9-vinylcarbazole)에 분산된 $ZnO/H_2Pc(I)_x$계의 광기전력 효과)

  • Heur, Soun-Ok;Kim, Young-Soon
    • Journal of the Korean Chemical Society
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    • v.39 no.3
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    • pp.176-185
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    • 1995
  • To improve photosensisitizing efficiency of ZnO/$H_2Pc(I)_x$ system, ZnO/$H_2Pc(I)_x$ system was dispersed in a typical photoconductive polymer of poly(9-vinylcarbazole)(PVCZ). The iodine dopant level(x) of ZnO/${\chi}-H_2Pc(I)_x$ is proportional to concentration of iodine, whereas x of ZnO/${\beta}-H_2Pc(I)_x$ decreased from the highest x=0.97 at more than $6.3{\times}10^{-3}$ M iodine solution. The Raman spectra of ZnO/${\chi}-H_2Pc(I)_x$ at 514 nm exhibited characteristic $I_3^-$ patterns in the range of 50∼550 $cm^{-1}$ at $x{\geq}0.57.$ The surface photovoltage of ZnO/${\chi}-H_2Pc(I)_{0.48}$/PVCZ was approximately 1.6 times greater than ZnO/${\chi}-H_2 Pc(I)_{0.48}$ and was 1.8 times of ZnO/${\chi}-H_2Pc(I)_{0.57}$/PVCZ at 670 nm. With ZnO/$H_2Pc(I)_x$/PVCZ, the highest iodine dopant levels showed a higher photovoltage. Therefore the injection of holes from H2Pc into PVCZ resulted in that photosensisitizing effect of ZnO/$H_2Pc(I)_x$/PVCZ system was improved compared to ZnO/$H_2Pc(I)_x$ case.

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Photo-induced Isomerization and Polymerization of (Z,Z)-Muconate Anion in the Gallery Space of [LiAl2(OH)6]+ Layers

  • Rhee, Seog-Woo;Jung, Duk-Young
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.35-40
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    • 2002
  • Photoreaction of guest organic anions in layered organic-inorganic hybrid materials was investigated. The layered hybrids were synthesized by an anion-exchange reaction of $[LiAl_2(OH)_6]Cl{\cdot}yH_2O$ layered double hydroxide with aqueous (Z,Z)- and (E,E)-muconates under inert atmospheric condition, to give new organicinorganic hybrids of $[LiAl_2(OH)_6]_2[(Z,Z)-C_6H_4O_4]{\cdot}zH_2O$ and $[LiAl_2(OH)_6]_2[(E,E)-C_6H_4O_4]{\cdot}H_2O$, respectively. The basal spacings calculated by XRPD of intercalates indicate that muconate anions have almost vertical arrangements against the host $[LiAl_2(OH)_6]^+$ lattices in the interlayer of organic-inorganic hybrid materials. When UV light was irradiated on the suspension of $[LiAl_2(OH)_6]_2[(Z,Z)-C_6H_4O_4]{\cdot}zH_2O$, the (Z,Z)-muconate anions of the gallery space of hybrids were polymerized in the aqueous media while it was isomerized into more stable (E,E)-muconate in the methanollic suspension in the presence of catalytic amount of molecular iodine. All the products were characterized using elemental analysis, TGA, XRPD, FT-IR, $^1H$ NMR and $^{13}C$ CP-MAS NMR.

Synthesis and Characterization of a Di-$\mu$-oxo-bridged Molybdeum(V) Complexes (두 개 산소가교형 몰리브덴(V) 착물의 합성과 그 성질에 관한 연구)

  • Doh, Gil Myung;Kim, Ill Chool;Choi, Bo Yong
    • Journal of the Korean Chemical Society
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    • v.39 no.3
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    • pp.198-203
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    • 1995
  • The Mo(V) $di-\mu-oxo$ type $(Mo_2O_4(H_2O)_2L)$ complexes $(L:\;C_3H_7CH(SCH_2COOH)_2,\;C_6H_5CH(SCH_2COOH)_2,\;CH_3OC_6H_4CH(SCH_2COOH)_2,\;C_5H_{10}C(SCH_2COOH)_2,\;C_3H_7C(CH_3)(SCH_2COOH)_2,\;C_3H_7CH(SCH_2CH_2COOH)_2,\;C_6H_5CH(SCH_2CH_2COOH)_2)$ have been prepared by the reaction of $[Mo_2O_4(H_2O)_6]^{2+}$ with a series of dithiodicarboxy ligands. These complexes are completed by two terminal oxygens arranged trans to one another and each ligand forms a chelate type between two molybdenum. In $Mo_2O_4(H_2O)_2L$, two $H_2O$ coordinated at trans site of terminal oxygens. The prepared complexes have been characterized by elemental analysis, infrared spectra, electronic spectra, and nuclear magnetic resonance spectra. In the potential range -0.00 V to -1.00 V at a scan rate of 20 $mVs^{-1}$, a cathodic peak at -0.50∼-0.58 V (vs. SCE) and an anodic peak at -0.40∼-0.43 V (vs. SCE) have been observed in aquous solution. The ratio of the cathodic to anodic current ($I_{pc}/I_{pa}$) is almost 1, we infer that redox is reversible reaction.

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Two-Dimensional Lanthanum-BDC Coordination Polymer:Hydrothermal Synthesis and Structure of [La4(BDC)6(H2O)5](H2O)(BDC=benzene-1,3-dicaboxylate) (2차원 La-BDC 배위 고분자: [La4(BDC)6(H2O)5](H2O)의 수열합성 및 구조(BDC=benzene-1,3-dicaboxylate))

  • Kim, Hye Jin;Min, Dong Won;Heo, Hyun Su;Lee, Soon W.
    • Journal of the Korean Chemical Society
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    • v.45 no.6
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    • pp.507-512
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    • 2001
  • The hydrothermal reaction between lanthanum(Ⅲ) nitrate $(La(NO3)3${\cdot}$6H_2O)$ and benzene-1,3-dicarboxylic acid $(H_2BDC)$ in the presence of 1,2-bis(4-pyridyl)ethane gave a 2-D lanthnum-BDC coordination polymer with an empirical formula of $〔La_4$(BDC)_6(H_2O)_5$〕(H_2O)$ (1). X-ray structure analysis of compound 1 revealed that this polymer contains four distinct La metals. The three La metals are 7-coordinate with three different structures: a capped trigonal prism, a capped octahedron, and a pentagonal bipyramid. The remaining La metal has a 8-coordinate, square antiprismatic structure.

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A Mechanistic Study on Reactions of Aryl Benzoates with Ethoxide, Aryloxides and Acetophenone oximates in Absolute Ethanol

  • 엄익환;오수진;권동숙
    • Bulletin of the Korean Chemical Society
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    • v.17 no.9
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    • pp.802-807
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    • 1996
  • Second-order rate constants have been measured spectrophotometrically for the reactions of aryl benzoates (X-C6H4CO2C6H4-Y) with EtO-, Z-C6H4O- and Z-C6H4C(Me)=NO- in absolute ethanol at 25.0 ℃. All the reactions have been performed in the presence of excess 18-crown-6 ether in order to eliminate the catalytic effect shown by alkali metal ion. A good Hammett correlation has been obtained with a large ρ- value (-1.96) when σ- (Z) constant was used for the reaction of p-nitrophenyl benzoate (PNPB) with Z-C6H4O-. Surprisingly, the one for the reaction of PNPB with Z-C6H4C(Me)=NO- gives a small but definitely positive ρ- value (+0.09). However, for reactions of C6H5CO2C6H4-Y with EtO-, correlation of log k with σ- (Y) constant gives very poor Hammett correlation. A significantly improved linearity has been obtained when σ0 (Y) constant was used, indicating that the leaving group departure is little advanced at the TS of the RDS. For reactions of X-C6H4CO2C6H4-4-NO2 with EtO-, C6H5O- and C6H5C(Me)=NO-, correlations of log k with σ (X) constants for all the three nucleophile systems give good linearity with large positive ρ values, e.g. 2.95, 2.81 and 3.06 for EtO-, C6H5O- and C6H5C(Me)=NO-, respectively. The large ρ values clearly suggest that the present reaction proceeds via a stepwise mechanism in which the formation of the addition intermediate is the RDS.

Paper-Electrophoretic Separation of Ruthenium Chloro-Complexes (전기영동에 의한 루테늄 염화착물의 분리)

  • Byung-Hun Lee;Cheon-Hwey Cho
    • Nuclear Engineering and Technology
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    • v.16 no.2
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    • pp.58-63
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    • 1984
  • Paper electrophoretic separation of octahedrally bonded (Ruc $l_{6}$ )$^{3-}$ has been carried out by using the specially designed migration apparatus. The supporting electrolyte solutions are as follows: 0.1M-HCl $O_4$, 0.05 M-HCl+0.09M-KCl, 0.1M-HCl, 5$\times$10$^{-3}$ M-NTA, 0.01M-HCl, 0.01M-HCl $O_4$, 0.01M-citric acid, 0.01M-K $H_2$P $O_4$+0.01M-N $a_2$HP $O_4$, 0.05M-borax, 0.025M-N $a_2$C $O_3$+0.025M-NaHC $O_3$, 0.01M-N $a_3$P $O_4$, 0.01M-NaOH and 0.1 M-NaOH. The (Ruc $l_{6}$ )$^{3-}$ appears in 2 to 4 peaks and is found in several chemical species such as (RuCl ($H_2O$)$_{5}$ )$^{2+}$, cis and trans (RuC $l_2$($H_2O$)$_4$)$^{1+}$, (RuC $l_3$($H_2O$)$_3$)$^{0}$ , (RuC $l_4$($H_2O$)$_2$)$^{1-}$, (RuC $l_{5}$ ($H_2O$))$^{2-}$ and (RuC $l_{6}$ )$^{3-}$. The retention value has been found to be highest in the 0.025M-N $a_2$C $O_3$+0.025M-NaHC $O_3$ electrolyte solution.n.

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3-Dimensional Terbium Coordination Polymers: [Tb4(NDC)6(H2O)5]·2H2O and [Tb2(BPDC)3(H2O)3]·H2O(NDC = 2,6-Naphthalenedicarboxylate; BPDC = 2,2'-Bipyridine-4,4'-dicarboxylate)

  • Min, Dong-Won;Lee, Soon-W.
    • Bulletin of the Korean Chemical Society
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    • v.23 no.7
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    • pp.948-952
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    • 2002
  • Three-dimensional terbium coordination polymers with the formulas of [Tb4(NDC)6(H2O)5]${\cdot}$2H2O (1) and [Tb2(BPDC)3(H2O)3]${\cdot}$H2O (2) (NDC = 2,6-naphthalenedicarboxylate; BPDC = 2,2'-bipyridine-4,4'-dicarboxy-late) were prepared by hydrothermal reactions. Both compounds were structurally characterized by X-ray diffraction. Compound 1 has a polymeric structure that contains four distinct Tb metals. Three Tb metals have a square-antiprismatic structure, and the remaining one has a 9-coordinate, triply capped trigonal-prismatic structure. Compound 2 is also a polymer with two distinct Tb metals, both of which have a square-antiprismatic structure. The pyridine nitrogen atoms of the BPDC 2- ligand do not coordinate to the metal centers in compound 2.

The Geometrical Isomerization on Acidification in Hexamolybdoheteropoly Oxometalate. The Crystal Structure of $(NH_{4})_{4.5}[H_{3.5}\alpha-PtMo_{6}O_{24}].\;1.5H_{2}O,\;(NH_{4})_{4}[H_{4}\beta-PtMo_{6}O_{24}].\;1.5H_{2}O,\;and\;K_{3.5}[H_{4.5}\alpha-PtMo_{6}O_{24}].\;3H_{2}O$

  • Lee, Uk;Yukiyoshi Sasaki
    • Bulletin of the Korean Chemical Society
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    • v.15 no.1
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    • pp.37-45
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    • 1994
  • $(NH_4)_{4.5}[H_{3.5}{\alpha}-PtMo_6O_{24}]{\cdot}1.5\;H_2O(A),\;(NH_4)_4[H_4{\beta}-PtMo_6O_{24}]{\cdot}1.5\;H_2O(B),\;and\;K_{3.5}[H_{4.5}{\alpha}-PtMo_6O_{24}]{\cdot}3\;H_2O(C)$ have been synthesized and their molecular structures have been also determined by single-crystal X-ray diffraction technique. The space groups, unit cell parameters, and R factors are as follows: Compound A, monoclinic, $A_{2/a}$, a= 19.074 (3), b=21.490 (3), c=15.183 (2) ${\AA};\;{\beta}$=109.67 (1) ${\AA}$; z=8; R=0.075($IF_0I>4{\sigma}(IF_0I);$ Compound B, triclinic, P$bar{1}$, a=10.776 (2), b=15.174 (4), c=10.697 (3) ${\AA};\;{\alpha}$ =126.29 (2), ${\beta}$=111.55 (2), ${\gamma}$=93.18 (2) ${\AA}$; Z=2; R=0.046($IF_0I>3{\sigma}(IF_0I);$): Compound C, triclinic, Pl, a=12.426 (2), b=13.884 (2), c=10.089 (1) ${\AA}$; ${\alpha}$=102.59 (2), ${\beta}$=110.73 (1), ${\gamma}$=53.93 (1) ${\AA}$; Z=2; R=0.074 ($IF_0I>3{\sigma}(IF_0I)$. Compounds A and C contain the well-known Anderson structure (planar structure) heteropoly oxometalate having approximate $bar{3}_m(D_{3d})$ symmetry, while compound B contains the bent structure heteropoly oxometalate having appproximate $2_{mm}(C2_v)$ symmetry. The bent structure and the planar one are geometrical isomers. These compounds are rot only novel heteroply molybdates containing platinate(IV) but also the first example of geometrical isomerism in the hexamolybdoheteropoly oxometalates. That isomerization surprisingly occurred because of the change of only 0.5 non-acidic hydrogen atom attached to the polyanion such as $[H_{3.5}{\alpha} -PtMo_6O_{24}]^{4.5-}{\to}[H_4{\beta}-PtMo_6O_{24}]^{4-}{\to}[H_{4.5}{\alpha} -PtMo_6O_{24}]^{3.5-}$. It seems that the gradual protonation of the polyanion plays an important role in that isomerism. These heteropolyanions form dimers by strong hydrogen bonds between two heteropolyanions in the respective crystal system.

Structural characterization of ladder-type cadmium(II) citrate complex, (C3H12N2)[{Cd(H2O)(C6H5O7)}2]·6H2O

  • Kim, Chong-Hyeak;Lee, Sueg-Geun
    • Analytical Science and Technology
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    • v.20 no.4
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    • pp.355-360
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    • 2007
  • The title complex, $(C_3H_{12}N_2)[\{Cd(H_2O)(C_6H_5O_7)\}_2]{\cdot}6H_2O$, I, has been prepared and its structure characterized by FT-IR, EDS, elemental analysis, ICP-AES, and X-ray single crystallography. It is triclinic system, $P{\bar{1}}$ space group with a = 10.236(2), b = 11.318(2), c = $13.198(2){\AA}$, ${\alpha}=77.95(1)^{\circ}$, ${\beta}=68.10(1)^{\circ}$, ${\gamma}=78.12(1)^{\circ}$, V = $1373.5(3){\AA}^3$, Z = 2. Complex I has constituted by protonated 1,3-diaminopropane cations, citrate coordinated cadmium(II) anions, and free water molecules. The central cadmium atoms have a capped trigonal prism geometry by seven coordination with six oxygen atoms of three different citrate ligands and one water molecule. Citrate ligands are bridged to three different cadmium atoms. Each cadmium atom is linked by carboxylate and hydroxyl groups of citrate ligand to construct an one-dimensional ladder-type assembly structure. The polymeric crystal structure is stabilized by three-dimensional networks of the intermolecular O-H${\cdots}$O and N-H${\cdots}$O hydrogen-bonding interaction.

Study on Formation and Properties of Dioxomolybdenum Complexes (디옥소몰리브덴 착물의 합성과 그 성질에 대한 연구)

  • Sang-Oh Oh;Bon-Kweon Koo
    • Journal of the Korean Chemical Society
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    • v.30 no.5
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    • pp.441-448
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    • 1986
  • Dioxobis(sub.-salicylaldiminato) molybdenum (VI) complexes, $MoO_2\;(X-sal-N-R)_2,\;(X=H,\;5-CH_3,\;R=C_6H_5,\;p-F-C_6H_4,\;m-Cl-C_6H_4,p-I-C_6H_4\;and\;p-C_2H_5-C_6H_4)$, have been prepared by reactions of dioxobis(sub.-salicylaldehydato) molybdenum (VI), $MoO_2(X-sal)_2$ with primary amines, in which $MoO_2(X-sal)_2$ complexes were obtained by acidification of a mixture solution of ammonium paramolybdate in water and appropriate salicylaldehyde in methanol. All these complexes show two strong Mo=O stretching imodes in the 900-940$cm^{-1}$ and p.m.r. spectra exhibited only one signal for the azomethine group. These results confirmed that the complexes are six-coordinated octahedron with a $cis-MoO_2$ group and the geometrical configurations of the complexes possess a C2 axis of symmetry. From the mass analyses of the complexes, it found that the composition ratios of $MoO_2$ : ligand are 1 : 2. The charge transfer transition corresponding to N-Mo, and O-Mo occured at 29,000$cm^{-1}$ and 32,000$cm^{-1}$ respectively. Where, the complexes were found to be non-ionic materials by conductivity measurements in dimethylformamide.

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