• Title/Summary/Keyword: Bipyridine

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Kinetics and Mechanism of the Oxidation of Substituted Benzyl Alcohols by Cr(VI)-4,4'-Bipyridine Complex (크롬(VI)-4,4'-Bipyridine 착물에 의한 치환 벤질 알코올류의 산화반응 속도론과 메카니즘)

  • Kim, Young-Sik;Park, Young-Cho
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.13 no.1
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    • pp.462-469
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    • 2012
  • Cr(VI)-4,4'-bipyridine complex(4,4'-bipyridinium dichromate) was synthesized by the reaction of 4,4'-bipyridine with chromium trioxide in H2O, and characterized by IR, ICP. The oxidation of benzyl alcohol using 4,4'-bipyridinium dichromate in various solvents showed that the reactivity increased with the increase of the dielectric constant(${\varepsilon}$), in the order: cyclohexene$CH_3$, H, m-Br, m-$NO_2$) smoothly in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.63(303K). The observed experimental data have been rationalized as follows; the proton transfer occurs after the prior formation of a chromate ester in the rate determining step.

Preparation and Photophysical Properties of 4-(9-Anthrylethenyl)-4'-methyl-2,2'-bipyridine and Its Ruthenium Bipyridyl Complex $[Ru(bpy)_2(t-aemb)](PF_6)_2$

  • 배은영;신은주
    • Bulletin of the Korean Chemical Society
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    • v.19 no.1
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    • pp.86-93
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    • 1998
  • Trans-4-(9-anthrylethenyl)-4'-methyl-2,2'-bipyridine(t-aemb) and its bipyridyl Ru complex $[Ru(bpy)_2(t-aemb)](PF_6)_2$ (bpy=2,2'-bipyridine) 1 have been prepared and their excited state properties have been studied. t-Aemb exhibits solvent-dependent fluorescence and efficient trans→cis photoisomerization. 1 shows very weak fluorescence and its photochemically reactive. Fluorescence is wavelength-dependent. While the excitation into the MLCT band makes the complex fluorescent, direct absorption by the t-aemb ligand leads to the photoreaction of t-aemb ligand and no fluorescence is observed. 1 is considered to behave in part as bichromophoric molecule in which $[Ru(bpy)_3](PF_6)_2$ and anthryl group are covalently linked by ethenyl linkage. Because anthryl moiety is not effectively conjugated with bipyridylethenyl moiety due to steric hindrance, weak fluorescence can be explained due to the efficient energy or electron transfer.

Redox Properties of Modified Poly-N,N'-bis(2-pyrrol-1-yl-propyl)-4,4'-Bipyridine Film Electrode (수식된 N,N'-bis(2-pyrrol-1-yl-propyl)-4,4'-bipyridine 고분자 피막전극의 산화-환원 특성)

  • Cha, Seong Keuck
    • Journal of the Korean Chemical Society
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    • v.45 no.5
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    • pp.429-435
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    • 2001
  • The monomer N,N'-bis(2-pyrrol-1-yl-propyl)-4,4'-bipyridine(bpb) was electrochemically polymerized on the glassy carbon electrode surface, which was modified with 1:1 ratio of erichrome black T(EBT) and glutathione(GSSG) to give a type of GC/poly-bpb, EBT, GSSG electrode for depositing Zn(II). The diffusion coefficients of the incorporated ions were 2.43${\times}10^{-15}$ and 9.14${\times}10^{-15} cm^2s^{-1}$ before taking Zn(II) ions and after them respectively. The modified electrodes are stable at the electrode process. The polymerized poly-bpb of 2.83${\times}10^4gmol^{-1}$ can deposit 2.15${\times}10^4gmol^{-1}$ of Zn(II). The number of pumping ions involving in the redox procedure at 0.77 V was 81.7% of the captured 180 ions into the polymer matrix, which was 3 times larger than that of the electrode modified with EBT alone.

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Dynamic Rapid Synthesis of Bis(2,2'-bipyridine)nitrato Zinc (II) Nitrate Using a Microwave Method and its Application to Dye-Sensitized Solar Cells (DSSC)

  • Kim, Young-Mi;Kim, Su-Jung;Nahm, Kee-Pyung;Kang, Mi-Sook
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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    • pp.2923-2928
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    • 2010
  • This study examined the synthesis of the crystal structure of bis(2,2'-bipyridine)nitrato zinc (II) nitrate, $[Zn(bipy)_2(NO_3)]^+NO_3^-$ using a microwave treatment at 300 W and 60 Hz for the application to dye-sensitized solar cells. The simulated complex structure of the complex was optimized with the density functional theory calculations for the UV-vis spectrum of the ground state using Gaussian 03 at the B3LYP/LANL2DZ level. The structure of the acquired complex was expected a penta-coordination with four nitrogen atoms of bipyridine and the oxygen bond of the $NO_3^-$ ion. The reflectance UV-vis absorption spectra exhibited two absorptions (L-L transfers) that were assigned to the transfers from the ligand ($\sigma$, $\pi$) of $NO_3$ to the ligand ($\sigma^*$, $\pi^*$) of pyridine at around 200 - 350 nm, and from the non-bonding orbital (n) of O in $NO_3$ to the p-orbital of pyridine at around 450 - 550 nm, respectively. The photoelectric efficiency was approximately 0.397% in the dye-sensitized solar cells with the nanometer-sized $TiO_2$ at an open-circuit voltage (Voc) of 0.39 V, a short-circuit current density (Jsc) of $1.79\;mA/cm^2$, and an incident light intensity of $100\;mW/cm^2$.

Electrocatalytic Effect on the Oxygen Reduction and Electrochemical Properties of Co(Ⅱ)-dimethyl Bipyridine Perchlorate (Co(Ⅱ)$(dimethyl bipyridine)_3(ClO_4)_2$의 전기화학적 성질과 산소환원에 대한 전극 촉매 효과)

  • Kim, Il Kwang;Park, Chong Sool;Han, Wan Soo;Kim, Youn Keun;Jeon, Il Cheol
    • Journal of the Korean Chemical Society
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    • v.41 no.8
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    • pp.385-391
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    • 1997
  • Diffusion Coefficient$(D_0)$ and electrode reaction rate Constant$(K_0)$ of Co$(dimethyl bipyridine)_3(ClO_4)_2$ were determined by cyclic voltammetry and chronoamperometry. It was also investigated that the effects of solvent, concentration, and scan rate, etc. on the diffusion coefficient and the temperature effect on the rate constant. The peak currents and diffusion coefficients were dcreased as increasing the viscosity of solvent. Diffusion coefficient was $5.54{\times}10^{-6 }cm^2/sec$ and the reaction rate constant was $2.39{\times}10^{-3 }/s$ at 25$^{\circ}C$. The thermodynamic parameters such as ${\Delta}G^{\neq},\;{\Delta}H^{\neq},\;and\;{\Delta}S$ were calculated from plotting the reaction rate constants versus the solution temperatures. This compound was shown the catalytic effect on the oxygen reduction that the reduction peak current of oxygen was greatly enhanced and the peak potential was shifted to +0.2 volt.

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A Study on CO Substitution of Group 6 Metal Carbonyls by Using Phase Transfer Catalyst(1) (상이동촉매에 의한 GROUP 6 금속카르보닐의 CO 치환에 관한 연구(1) : 용매와 촉매종류에 의한 영향)

  • Yang, Hyun S.;Park, Ha S.
    • Applied Chemistry for Engineering
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    • v.3 no.1
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    • pp.72-80
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    • 1992
  • Group 6 $M(CO)_4$(2, 2'-bipyridine)[M=Cr, Mo, W] was synthesized by substituting CO ligand of $M(CO)_6$ with strong electron donating ligand, 2, 2'-blpyridine, in the presence of phase transfer catalyst. The effective of catalyst and solvent on the product yield were discussed according to concentration and kinds of catalyst, kinds of center cation and anion, type of alkyl and aryl groups attached to the center cation, and different chain length.

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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.