• Title/Summary/Keyword: Isostructural Temperature

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A Series of 3D Lanthanide Complexes Containing (La(III), Sm(III) and Gd(III)) Metal-organic Frameworks: Synthesis, Structure, Characterization and Their Luminescent Properties

  • Zhang, Huai-Min;Yang, Hao;Wu, Lan-Zhi;Song, Shuang;Yang, Li-Rong
    • Bulletin of the Korean Chemical Society
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    • v.33 no.11
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    • pp.3777-3787
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    • 2012
  • Three kinds of 3D isomorphous and isostructural coordination polymers, namely, $\{[Ln_2(PDA)_3(H_2O)_3]{\cdot}0.25H_2O\}_{\infty}$ (Ln = La(1), Sm(2), and Gd(3)) ($PDA^{2-}$ = pyridine-2,6-dicarboxylate anion) have been synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectroscopy, thermal analyses and single crystal X-ray diffraction. In these MOFs, Ln(III) centers adopt eight-coordinated and nine-coordinated with the $N_1O_7$ and $N_2O_7$ donor sets to construct distorted trianglar dodecahedron geometry and tricapped trigonal prism configurations, respectively. Based on the building block of tetranuclear homometallic $Ln_4C_4O_8$ unit (16-membered ring), 1-3 are connected into highly ordered 2D sheets via O-C-O linkers and further constructed into 3D architectures through hydrogen bonds. Crystallographic parameters suggest that the lanthanide contraction effect exist in these coordination polymers. Luminescent properties of the lanthanide-based MOFs (metal-organic frameworks) have been measured at room temperature, which reveal that they presenting ionselective characters toward certain metals, such as $Mg^{2+}$, $Cd^{2+}$ and $Pb^{2+}$ ions.

Structural and Magnetic Studies on Electrochemically Lithiated $PrBa_2Cu_3O_y$

  • Choy, Jin-Ho;Chun, Sung-Ho;Kang, Seong-Gu
    • Bulletin of the Korean Chemical Society
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    • v.11 no.6
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    • pp.564-567
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    • 1990
  • A lithiated compound $Li_{0.1}Pr^{3+}Ba_2Cu_3O_y$ has been successfully prepared by electrochemical method, which is achieved with a two electrode cell of the type: Metal(Li)/($Li^+\;,\;ClO_4^-$) + propylene carbonate/$PrBa_2Cu_3O_y$. All Pr ions in the lithiated compound are stabilized with a trivalent state as the other rare earths (Ⅲ) substituted in the 90K superconductor lattice ($Y_{1-x}Ln_x^-Ba_2Cu_3O_{7-{\delta}}$). Powder X-ray diffraction analysis shows that both compounds, $PrBa_2Cu_3O_y$ and $Li_{0.1}PrBa_2Cu_3O_y$ are isostructural with the 90 K superconductor, ($YBa_2Cu_3O_{7-{\delta}}$), nevertheless both of them are non-metallic and also non-superconducting down to 10 K. Magnetic susceptibility ${\chi}$ vs. temperature data indicate that Curie contribution from the magnetic ions (Pr and Cu) is weakened on the one hand, but on the other hand temperature-independent part of susceptibility ${\chi}_o$ increases depending upon the rate of lithium intercalation in $PrBa_2Cu_3O_y$ lattice.

Solubilization of Monochlorophenol Isomers by the Aqueous Solution of Tetradecyltrimethylammonium bromide (Tetradecyltrimethylammonium bromide 수용액에서 Monochlorophenol 이성질체들의 가용화에 대한 연구)

  • Lee, Byung-Hwan
    • Applied Chemistry for Engineering
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    • v.21 no.3
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    • pp.337-342
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    • 2010
  • The interaction of monochlorophenol isomers with the micellar system of TTAB (tetradecyltrimethylammonium bromide) was studied by the UV/Vis spectrophotometric method. The solubilization constants ($K_s$) of monochlorophenol isomers into this micellar system have been measured with the change of temperature. Various thermodynamic parameters (${\Delta}G^{\circ}_s$, ${\Delta}H^{\circ}_s$, and ${\Delta}S^{\circ}_s$) have been calculated and analyzed from the dependence of $K_s$ values on the temperature. The results show that the values of ${\Delta}G^{\circ}_s$ and ${\Delta}H^{\circ}_s$ are all negative but the values of ${\Delta}S^{\circ}_s$ are all positive for the solubilizations of all isomers within the measured temperature range. The effects of additives (n-butanol and NaCl) on the solubilization of monochlorophenol isomers by the same surfactant system have been also measured. There was a great change on the values of $K_s$ and CMC simultaneously with these additives. From these changes we can postulate the solubilization sites of each isomer in the micellar system of TTAB.

Synthesis, Characterization, Luminescence and Biological Activity of Two Lanthanide Complexes Involving Mixed Ligands

  • Ma, De-Yun;Guo, Hai-Fu;Qin, Liang;Xu, Jun
    • Bulletin of the Korean Chemical Society
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    • v.34 no.9
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    • pp.2774-2780
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    • 2013
  • Two new isostructural dinuclear complexes, $Ln_2(4-cpa)_6(bpy)_2$ (Ln = Eu (1); Tb (2), 4-cpa = 4-chlorophenylacetate, bpy = 2,2'-bipyridine), have been hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffraction and single-crystal X-ray diffraction. The lanthanide ions are bridged by two bidentate and two terdentate carboxylate groups to give centrosymmetric dimers with $Ln{\cdots}Ln$ separations of 3.967(2) and 3.956(3) ${\AA}$, respectively. Each metal atom is nine-coordinate and exhibits a distorted tricapped trigonal prismatic geometry. Three-dimensional fluorescence spectra show that both 1 and 2 emit bright red and green luminescence at room temperature, with long lifetimes of up to 0.369 ms (at 614 nm) and 0.432 ms (at 543 nm), respectively. Moreover, poor luminescence efficiency has been noted for complex 2. The 4-Hcpa ligand and complexes 1-2 have been screened for their phytogrowth-inhibitory activities against Brassica napus L. and Echinochloa crusgalli L., and the results are compared with the activity of quizalofop-P-ethyl.

Microwave-assisted Preparation, Structures, and Photoluminescent Properties of [Ln(NO3)2(H2O)3(L)2](NO3)(H2O) {Ln=Tb, Eu;L=2-(4-pyridylium)ethanesulfonate, (4-pyH)+-CH2CH2-SO3-}

  • Zheng, Zhen Nu;Lee, Soon-W.
    • Bulletin of the Korean Chemical Society
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    • v.32 no.6
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    • pp.1859-1864
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    • 2011
  • Two lanthanide complexes, $[Ln(NO_3)_2(H_2O)_3(L)_2](NO_3)(H_2O)$ {Ln = Eu (1), Tb (2); L = 2-(4-pyridylium)-ethanesulfonate, $(4-pyH)^+-CH_2CH_2-SO_3^-)$}, were prepared from lanthanide nitrate and 4-pyridineethanesulfonic acid in $H_2O$ under microwave-heating conditions. Complexes 1 and 2 are isostructural, and the lanthanide metal in both complexes is coordinated to nine oxygen atoms. The pyridyl nitrogen in the ligand is protonated to give a zwitter ion that possesses an $NH^+$ (pyridyl) positive end and an $SO_3^-$ negative end. All O-H and N-H hydrogen atoms participate in hydrogen bonds to generate a two-dimensional (complex 1) or a three-dimensional network (complex 2). Complex 1 exhibits an intense red emission, whereas complex 2 exhibits an intense green emission in the solid state at room temperature.

Novel Lanthanide Coordination Polymers Prepared by Microwave Heating: [Ln(L)3(H2O)2](H2O)3 (Ln = Eu, Tb, Gd; L = trans-(3-py)-CH=CH-COO)

  • Han, Sun-Hwa;Zheng, Zhen Nu;Cho, Sung-Il;Lee, Soon-W.
    • Bulletin of the Korean Chemical Society
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    • v.33 no.6
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    • pp.2017-2022
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    • 2012
  • Three isostructural lanthanide coordination polymers, $[Ln(L)_3(H_2O)_2](H_2O)_3$ {Ln = Eu (1), Tb (2), Gd (3); L = $trans$-3-(3-pyridyl)acrylate, (3-py)-CH=CH-COO}, were prepared from HL, lanthanide nitrate, and NaOH in $H_2O$ by microwave heating. In all coordination polymers, the metal is bonded to eight oxygen atoms, and all pyridyl nitrogen atoms do not coordinate to the metals. All polymers have a 1-D loop-connected chain structure. The hydrogen atoms in the aqua ligands and lattice water molecules all participate in the hydrogen bonds of the O-$H{\cdots}O$ or O-$H{\cdots}N$ type. The hydrogen bonds connect the 1-D chains to create a 2-D network. Polymer 1 exhibited red luminescence in the solid state at room temperature.

Solubilization of 4-Alkylbenzoic Acid Isomers by the Aqueous Solution of Tetradecyltrimethylammonium Bromide (테트라데실트리메틸암모늄 브로마이드의 수용액에서 4-알킬벤조산 이성질체들의 가용화에 대한 연구)

  • Lee, Nam-Min;Lee, Byung-Hwan
    • Journal of the Korean Chemical Society
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    • v.56 no.2
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    • pp.188-194
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    • 2012
  • The interaction of 4-alkylbenzoic acid isomers with the micellar system of TTAB (tetradecyltrimethylammonium bromide) was studied by the UV/Vis spectrophotometric method. The solubilization constants ($K_s$) of 4-alkylbenzoic acid isomers into the TTAB micellar system and the critical micelle concentration (CMC) of TTAB have been measured with the change of temperature. Various thermodynamic parameters have been calculated and analyzed from those measurements. The results show that the values of ${\Delta}G^o{_s}$ for the solubilization of all the isomers are negative and the values of ${\Delta}H^o{_s}$ and ${\Delta}S^o{_s}$ are all positive within the measured temperature range. The effects of additives (n-butanol and NaCl) on the solubilization of 4-alkylbenzoic acid isomers have been also measured. There was a great change on the values of $K_s$ and CMC simultaneously with these additives. From these changes we can postulate that the solubilization sites of 4-alkylbenzoic acids are the core or deep palisade region of the TTAB micelle.

Study on the Solubilizations of Dichlorophenol Isomers by the Cationic Surfactant Solution (양이온성 계면활성제의 수용액에서 Dichlorophenol 이성질체들의 가용화에 대한 연구)

  • Lee, Nam-Min;Lee, Byung-Hwan
    • Journal of the Korean Chemical Society
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    • v.54 no.4
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    • pp.374-379
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    • 2010
  • The interaction of dichlorophenol isomers with the micellar system of TTAB (tetradecyltrimethylammonium bromide) was studied by the UV/Vis spectrophotometric method. The solubilization constants ($K_s$) of dichlorophenol isomers into the micellar system have been measured with the change of temperature and the various thermodynamic parameters have been calculated and analyzed from these changes. The results show that the values of ${\Delta}G^{\circ}_s$ and ${\Delta}H^{\circ}_s$ are all negative within the measured temperature range. The effects of additives (n-butanol and NaCl) on the solubilization of dichlorophenol isomers have been also measured. There was a great change on the values of $K_s$ and CMC simultaneously with these additives. From these changes we can postulate the solubilization sites of each isomers in the micellar system of TTAB.

Solubilization of Para-Halogenated Benzoic Acid Isomers by the Solution of Tetradecyltrimethylammonium Bromide (Tetradecyltrimethylammonium Bromide 용액에서 Para-할로겐화 벤조산 이성질체들의 가용화에 대한 연구)

  • Lee, Nam-Min;Lee, Byung-Hwan
    • Applied Chemistry for Engineering
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    • v.22 no.5
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    • pp.473-478
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    • 2011
  • The interaction of para-halogenated benzoic acid isomers with the micellar system of tetradecyltrimethylammonium bromide was studied by the UV/Vis spectrophotometric method. The solubilization constants ($K_s$) of benzoic acid isomers into the micellar system of TTAB and the critical micelle concentration (CMC) of TTAB have been measured with the change of temperature. Various thermodynamic parameters have been calculated and analyzed from those measurement. The results show that the values of ${\Delta}G^{\circ}{_s}$ for the solubilization of all isomers are negative and the values of ${\Delta}H^{\circ}{_s}$ and ${\Delta}S^{\circ}{_s}$ are all positive within the measured temperature range. The effects of additives (n-butanol and NaCl) on the solubilization of benzoic acid isomers have been also measured. There was a great decrease on the values of $K_s$ and CMC simultaneously with these additives. From these changes we can postulate that the solubilization sites of each isomers in the TTAB micellar system are the surface or the palisade region of the micelle.

Relationship between the Micellization of TTAB and the Solubilization of p-Bromophenol in TTAB Solution (TTAB 용액에서 p-브로모페놀의 가용화와 TTAB의 미셀화와의 상관관계에 대한 연구)

  • Lee, Byung-Hwan
    • Journal of the Korean Chemical Society
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    • v.57 no.6
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    • pp.665-671
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    • 2013
  • The solubilization of p-bromophenol by the micellar system of TTAB(tetradecyltrimethylammonium bromide) and the micellization of TTAB were studied by the UV-vis spectrophotometric method simultaneously. And the effects of temperature on these properties have been measured for the thermodynamic study. The results show that the ${\Delta}G_s{^o}$ and ${\Delta}H_s{^o}$ values are negative and the ${\Delta}S_s{^o}$ values are positive for the solubilization of p-bromophenol within the measured range. On the other hand, the ${\Delta}G_m{^o}$ values are negative and the ${\Delta}H_m{^o}$ and ${\Delta}S_m{^o}$ values are positive for the micellization of TTAB. The effects of additives such as n-butanol and NaCl have been studied also for both properties and the relationship between these two properties has been also studied. From the results, we can postulate the solubilization site of p-bromophenol in the micelle.