• Title/Summary/Keyword: 2,2-Bipyridine

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pH and Micellar Effects on the Quenching of Tris(2,2'-bipyridine)Ruthenium(Ⅱ) Luminescence by 1-Alkyl-4,4'-bipyridinium : Evidence of Deep Enbedment of the Quencher Cations in Sodium Dodecyl Sulfate Micelle

  • 박준우;김유나
    • Bulletin of the Korean Chemical Society
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    • v.18 no.2
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    • pp.185-189
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    • 1997
  • The effect of pH and sodium dodecyl sulfate (SDS) micelle on the quenching of Ru(bpy)32+ luminescence by N-alkyl-4,4'-bipyridinium ions (RBPY+: R=methyl, octyl, dodecyl, benzyl) were investigated. In the absence of SDS, the quenching rate at pH 2 is similar to that of the corresponding methylalkyl viologens and much greater than that in pH 8 solution due to greater reducibility of the protonated form of RBPY+ (HRBPY2+). The quenching rate at pH 2 is strongly enhanced by the presence of SDS, while that at basic pH is greatly retarded. These observations are explained by deep embedment of RBPY+ into the hydrophobic hydrocarbon region of the micelle, whereas Ru(bpy)32+ and HRBPY2+ locate in the Stern layer of the micelle.

Oxidation of Benzyl Alcohols with Extraordinarily High Kinetic Isotope Effects

  • Jo, Myeong-Ran;Seok, Won-K.
    • Bulletin of the Korean Chemical Society
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    • v.32 no.spc8
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    • pp.3003-3008
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    • 2011
  • Reactions of benzyl alcohol and its derivatives by [Ru$^{IV}$(tpy)(dcbpy)(O)]$^{2+}$ (tpy = 2,2':6',2"-terpyridine; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) leading to the corresponding benzaldehydes in acetonitrile and water have been studied. Kinetic studies show that the reaction is first-order in both alcohol and oxidant, with k = 1.65 (${\pm}$ 0.1) $M^{-1}s^{-1}$ at $20^{\circ}C$, ${\Delta}H^{\ddag}$ = 4.3 (${\pm}$ 0.1) kcal/mol, ${\Delta}S^{\ddag}$ = -22 (${\pm}$ 1) eu, and $E_a$ = 4.9 (${\pm}$ 0.1) kcal/mol. High ${\alpha}$ C-H kinetic isotope effects are observed, but O-H solvent isotope effects are negligible. Spectral evidences with the isotope effects suggest that oxidation of benzyl alcohols occurs by a two-electron, hydride transfer. The catalytic cycles of aerobic benzyl alcohol oxidation are employed.

A Study for Mechanism and Oxidation Reaction of Substituted Benzyl Alcohols by 2,2'-Bipyridinium Chlorochromate (2,2'-Bipyridinium Chlorochromate에 의한 치환 벤질 알코올류의 산화반응과 메카니즘에 관한 연구)

  • Kim, Young-Sik;Park, Young-Cho
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.13 no.7
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    • pp.3252-3260
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    • 2012
  • 2,2'-Bipyridinium chlorochromate[$C_{10}H_8N_2HCrO_3Cl$] was synthesized by the reaction of 2,2'- bipyridine with chromium(VI) trioxide in 6M HCl. The structure was characterized by IR and ICP analysis. The oxidation of benzyl alcohol using 2,2'-bipyridinium chlorochromate in various solvents showed that the reactivity increased with the increase in the order of the dielectric constant(${\varepsilon}$), in the order: cyclohexene< chloroform$p-CH_3$, H, m-Br, $m-NO_2$) in N,N'-dimethylformamide. Electron-donating substituents accelerated the reaction, whereas electron acceptor groups retarded the reaction. The Hammett reaction constant(${\rho}$) was -0.64(303K). The oxidation reactivity of alcohols can be a useful factor to study about physical properties such as thermal stability, when the polysilsesquioxane solution is ready for an applying coating agent. The observed experimental data was used to rationalized the hydride ion transfer in the rate-determining step.

Synthesis and $^1$H-nmr of N-Arylated Nitrogen-Containing Aromatic Heterocycles

  • Koh Park, Kwang-Hee;Lee, Jae-Bong;Han, Du-Hee
    • Bulletin of the Korean Chemical Society
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    • v.6 no.3
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    • pp.141-144
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    • 1985
  • N-Arylation reaction of nitrogen-containing heterocycles such as pyridine, nicotinamide and 4,4'-bipyridine was studied. We prepared N-2,4-dinitrophenyl derivatives initially by reacting the above heterocycles with 2,4-dinitrochlorobenzene in ethanol, and then treated the N-2,4-dinitrophenylated heterocycles with various aniline derivatives, $XC_6H_4NH_2$(X = -H, p-$CH_3$, p-$C_2H_5$, p-Cl, p-CN, p-OH, p-$OCH_3$, o-Cl, m-$CH_3$) to yield the corresponding N-arylated compounds in fairly good yields. $H^1$-nmr patterns and peak assignments of the N-arylated products were described.

Noncovalently Linked Zinc Porphyrin-Ru(bpy)3 Dyad Assembled via Axial Coordination

  • Kim, Dol;Shin, Eun-Ju
    • Bulletin of the Korean Chemical Society
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    • v.24 no.10
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    • pp.1490-1494
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    • 2003
  • Noncovalently linked electron donor-acceptor dyad consisting of zinc tetratolylporphyrin and pyridine appended ruthenium trisbipyridine comlex was prepared, via axial coordination of pyridine moiety in ruthenium trisbipyridine complex on zinc tetratolylporphyrin. For the purpose of comparison, axial coordination of pyridine-appended 2,2'-bipyridine on zinc tetratolylporphyrin was also investigated. The Kvalues were detemined based on absorption of fluorescence studies. The fluorescence of zinc teratolylporphrin was efficiently quenched upon axial coordination of pyridine moiety, prbably due to the photoinduced electron transfer from zinc tetrtolylporphyrin to ruthenium trisbipyridine, supported by free enegy estimation.

Lanthanide-Oxalate Coordination Polymers Formed by Reductive Coupling of Carbon Dioxide to Oxalate: [Ln2(3,5-pdc)2(C2O4)(H2O)4]·2H2O (Ln = Eu, Sm, Ho, Dy; pdc = Pyridinedicarbox

  • Huh, Hyun-Sue;Lee, Soon W.
    • Bulletin of the Korean Chemical Society
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    • v.27 no.11
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    • pp.1839-1843
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    • 2006
  • Hydrothermal reactions of $Ln(NO_3)_3{\cdot}5H_2O $ (Ln = Eu (1), Sm (2), Ho (3), Dy (4)) with 3,5-pyridinedicarboxylic acid (3,5-pdcH2) in the presence of 4,4'-bipyridine led to the formation of the 3-D Ln(III)-coordination polymers with a formula unit of $[Ln_2(3,5-pdc)_2(C_2O_4)(H_2O)_4]{\cdot}2H_2O$. These polymers contain a bridging oxalate ligand ($C_2O_4\;^2$). On the basis of GCMS study of the mother liquor remaining after the reaction, we proposed that the $C_2O_4\;^2$ formation proceeds in three steps: (1) Ln(III)-mediated decarboxylation of $3,5-pdcH_2$ to give $CO_2$, (2) the reduction of $CO_2$ to $CO_2\;^{\cdot}$ by the Ln(II) species, and (3) the reductive coupling of the two $CO_2\;^{\cdot}$ radicals to the oxalate ($C_2O_4\;^2$) ion. All polymers were structurally characterized by X-ray diffraction.

One-Pot Synthesis, Crystal Structures and Thermal Properties of Two Three-Dimensional Cobalt(II) Complexes

  • Tao, Bo;Lei, Wen;Cheng, Feiran;Xia, Hua
    • Bulletin of the Korean Chemical Society
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    • v.33 no.6
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    • pp.1929-1933
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    • 2012
  • Two cobalt(II) compounds $[Co(2,2{^\prime}-bipy)(H_2O)_2(SO_4)]_n$ (1) and $[Co_2(2,2^{\prime}-bipy)_2(btec)(H_2O)_6]{\cdot}2H_2O$ (2) (2,2'-bipy = 2,2'-bipyridine, $H_4btec$ = 1,2,4,5-benzenetetracarboxylic acid), have been simultaneously synthesized by a one-pot slow solvent evaporation reaction. Their structures were determined by single-crystal X-ray diffraction and further characterized by X-ray powder diffraction (XRPD), IR, elemental and thermogravimetric analysis (TGA). The structural analysis reveals that compound 1 exhibits an infinite 1D chain structure with the octahedral Co(II) centers bridging by the tetrahedral ${\mu}_2-SO{_4}^{2-}$ ligands, while compound 2 possesses a dinuclear $Co_2(2,2^{\prime}-bipy)_2(btec)(H_2O)_6$ unit and the two adjacent octahedral Co(II) ions are linked by the bismonodentately coordinated btec ligand. Additionally, compound 2 exhibits blue fluorescent emission in the solid state at room temperature.

Synthesis, Crystal Structures and Properties of Two Binuclear Supramolecular Complexes Based on Biphenyl-2,2'-dicarboxylic Acid Ligand

  • Tang, Jin-Niu;Pan, Gang-Hong;Li, Long;Tian, Wei-Man;Huang, Zhong-Jing
    • Bulletin of the Korean Chemical Society
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    • v.34 no.2
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    • pp.374-378
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    • 2013
  • Two novel binuclear metal-organic coordination complexes [$Cd_2(Hdpa)_4(bpy)_2$] (1), [$Dy_2(dpa)_2(bpy)_2(NO_3)_2-(H_2O)_2$](bpy) (2) (where $H_2dpa$ = biphenyl-2,2'-dicarboxylic acid, bpy = 2,2'-bipyridine) have been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction, spectral method (IR), elemental analysis (EA), powder X-ray diffraction (XRD), electronic spectra (UV-vis), fluorescent in the solid state and thermogravimetric analysis (TGA). Complexes 1-2 crystallizes isomorphously in the Triclinic space group P-1. The ${\pi}-{\pi}$ stacking interactions and hydrogen-bonds play a vital role in determining the crystal packing and construction of the extended 3-D supramolecular network.

Crystal Structures and Thermal Properties of Two Binuclear Cd(II) Supramolecular Complexes Based on Quinolinecarboxylate Ligand

  • Hao, Hu-Jun;Yin, Xian-Hong;Lin, Cui-Wu;Wei, Shui-Qiang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3255-3260
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    • 2011
  • Two novel binuclear metal-organic coordination complexes $[Cd_2(L)_2(bpy)_2(H_2O)_2]{\cdot}6H_2O$ (1), $[Cd_2(L)_2(phen)_2-(H_2O)_2]{\cdot}2H_2O$ (2) (where L = 2-methylquinoline-3,4-dicarboxylate dianion, bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline) have been synthesized under hydrothermal conditions and characterized by single crystal Xray diffraction, spectral method (IR), elemental analysis and thermal gravimetric analysis (TGA). Both 1 and 2 consist of two Cd(II) atoms bridged by two monoatomic bridging carboxylate groups from two L ligands, and the second carboxylate group of each L is monodentately coordinated to Cd(II), creating a sevenmembered chelating ring. The coordination at each metal nucleus is completed by a water molecule and a chelating bidentate molecule. The 3D structures of the complexes are stabilized by ${\pi}-{\pi}$ stacking interactions and hydrogen-bonds.

Synthesis, Structures and Properties of Two Metal-organic Frameworks Derived from 3-Nitro-1,2-benzenedicarboxylic Acid

  • Xu, Wen-Jia;Zhang, Ling-Yu;Tang, Jin-Niu;Wang, Dai-Yin;Pan, Gang-Hong;Feng, Yu
    • Bulletin of the Korean Chemical Society
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    • v.34 no.8
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    • pp.2375-2380
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    • 2013
  • Two metal-organic frameworks based on the connectivity co-effect between rigid benzenedicarboxylic acid and bridging ligand have been synthesized $[Zn_2(3-NO_2-bdc)_2(4,4'-bpy)_2H_2O]_n$ (1), $[Co(3-NO_2-bdc)(4,4'-bpy)H_2O]_n$ (2) (where $3-NO_2-bdcH_2$ = 3-nitro-1,2-benzenedicarboxylic acid, 4,4'-bpy = 4,4'-bipyridine). The two novel complexes were characterized by IR spectrum, elemental analysis, fluorescent properties, thermogravimetric analysis, single-crystal X-ray diffraction and powder X-ray diffraction (PXRD). X-ray structure analysis reveals that 1 and 2 are two-dimensional (2D) network structures. Complex 1 and complex 2 belong to triclinic crystal with P-1 space group. The luminescence measurements reveal that two complexes exhibit good fluorescent emissions in the solid state at room temperature. Also, thermal decomposition process and powder X-ray diffraction of complexes were investigated.