• Title/Summary/Keyword: 배위

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Luminescence Studies of N-Methyllutidone, an Unusually High Triplet Energy Sensitizer (N-메틸루티돈의 루미네센스에 관한 연구)

  • Sang Chul Shim;Myung Ho Hyun;Kuy Ho Chae
    • Journal of the Korean Chemical Society
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    • v.22 no.1
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    • pp.45-51
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    • 1978
  • The luminescence of N-methyllutidone is studied in ethanol matrix at $77^{\circ}C$K. No fluorescence is observed but a strong phosphorescence with the quantum yield of 0.1 and the lifetime of 0.2 sec is recorded. An unusually high triplet energy of 85.1 kcal/mole is determined for the compound from the O-O band of phosphorescence. The cis ${\leftrightarrow}$ trans photoisomerization of high triplet energy olefins such as 2-hexene and trans-1,4-dichlorobutene-2 is efficiently sensitized by N-methyllutidone substantiating the high triplet energy of the compound. The negative polarization of O-O band reveals the emitting triplet state to be $({\pi},{\pi}^*)^3$ state. Alkaline metal salts such as lithium chloride enhances the phosphorescence intensity through cation-N-methyllutidone coordination widening the gap between $({\pi},{\pi}^*)^3$and $(n,{\pi}^*)^3$ states.

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Determination of Reactivity by MO Theory (XXIII). Substituent Effect on Regioselectivity of Diels-Alder Reactions (分子軌道論에 의한 反應性 決定 (제23보). Diels-Alder 反應의 配向性에 미치는 置換基 效果)

  • Ikchoon Lee;Eun Sook Han;Keun Bae Rhyu
    • Journal of the Korean Chemical Society
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    • v.26 no.1
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    • pp.7-17
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    • 1982
  • In order to predict substituent and Lewis acid effects on the regiospecificity of the Diels-Alder reaction, and to investigate the competition for the complexation of Lewis acid between diene and dienophile, frontier orbital theory has been applied to thermal and catalyzed Diels-Alder reaction by means of CNDO/2 MO method. It has been found that: (1) Lewis acid coordinated preferentially with diene rather than dienophile when carbonyl oxygen of acetoxy substituted diene had larger negative atomic charges than that of dienophile. (2) Most of the reaction were neutral electron demand type, and hence 4-C, 2-C and quantitative secondary orbital interacion methods were generally in good accord with experiments. (3) Sulfur activated the adjacent terminal carbon atom greatly to increase diene LUMO-dienophile HOMO interaction through vacant-d-orbital participation, and played an important role in controlling regioselectivity of neutral electron demand reaction type.

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Synthesis and Spectroscopic Characterization of Vanadium-Incorporated V-AlMCM-48 Mesoporous Material (바나듐이 들어있는 Mesoporous V-AlMCM-48 분자체의 합성 및 분광학적 특성 조사)

  • Back, Gernho;Yu, Jong-Sung;Park, Sung-Kun;Lee, Chul Wee;Won, Taejin
    • Korean Chemical Engineering Research
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    • v.44 no.4
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    • pp.369-374
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    • 2006
  • A solid-state reaction of $V_2O_5$ with AlMCM-48 followed by calcination generated very weak paramagnetic $VO^{2+}$ species in the mesoporous material. Dehydration and subsequent reduction with CO result in the formation of vanadyl $VO^{2+}$ species that can be characterized by EPR. The chemical environment of vanadium centers in $VO^{2+}-AlMCM-48$ was investigated by XRD, EDX, DR-UV-Vis, EPR,$^{29}Si$ and $^{27}Al$ and $^{51}V$ NMR. Vanadium species in MCM-48 are existed as pseudotetrahedral $VO^{2+}$ state when they were dehydrated or reduced with CO. The coordination of water on vanadyl ions transformed their structure to distorted octahedral.

A Synthesis and Characterization of Pt(II) Complexes with Bipyrimidin-based Back-bone System (비피리미딘계 배위자를 골격으로 하는 Pt(II)착체의 합성 및 특성)

  • Son, Seokhwan;Ahn, Hogeun;Chung, Minchul
    • Korean Chemical Engineering Research
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    • v.54 no.4
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    • pp.555-559
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    • 2016
  • In this study, new platinum complexes were synthesized utilizing the ligand of a 2,2'-bispyrimidine (bpim), 2,2'-bipyridine (bpy), 5,5'-dimethyl-2,2'-bipyridine (5,5-mebpy), 5'-bromo-2,2'-bipyridine (5-brbpy), 5,5'-dibromo-2,2'-bipyridine (5,5-brbpy), 4,4'-dimethyl-2,2'-bipyridine (4,4-mebpy), 4,4'-dihexyl-2,2'-Bipyridine (4,4-hebpy), 1,10'-Phenanthroline (phen), 3,4,7,8'-tetramethyl-1,10'-Phenanthroline (3,4,7,8-phen). In order to determine chemical structure of Synthesized platinum complexes, $^1H(^{13}C)$-NMR, UV-vis and FT-IR were used and optical physics and chemical properties were measured PL. In the case of platinum complexes, wavelength has been identified 356~421 nm. Quantum efficiency in DMSO solution was appeared 0.05~0.46.

Catalytic Performance of V-KIT-6 for the Oxidation of Styrene (스티렌 산화반응에 대한 V-KIT-6의 촉매특성 고찰)

  • Kim, Sang-Yun;Jermy, Balasamy R.;Bineesh, Kanattukara V.;Lim, Dong-Ok;Kim, Kyung-Hoon;Park, Dae-Won
    • Korean Chemical Engineering Research
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    • v.47 no.3
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    • pp.275-280
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    • 2009
  • The direct incorporation of vanadium into the three-dimensional(3-D) cubic Ia3d mesostructure designated as V-KIT-6 was carried out hydrothermally using a Pluronic P123 and n-butanol as the structure-directing mixture, tetraethylorthosilicate(TEOS) as the silica source and $NH_4VO_3$ as the vanadium source. The obtained V-KIT-6 showed a very high specific surface area ${\sim}1,000m^2/g$ with tunable pore diameters in narrow distribution of sizes ~6.0 nm. The coordination and nature of V sites in V-KIT-6 are characterized by $^{51}V$-spin-echo NMR analysis. The calcined V-KIT-6 materials showed excellent catalytic activity in the direct oxidation of styrene using tert-butyl hydroperoxide(TBHP) as an oxidant.

Study of Complex Formation of Dioxouranium(VI) Ion with Nitrate Ion by 17O NMR Spectroscopy (산소-17 핵자기공명분광법을 이용한 디옥소우라늄(VI) 이온의 질산 이온과의 착물형성에 관한 연구)

  • Jung, Woo-Sik
    • Applied Chemistry for Engineering
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    • v.3 no.2
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    • pp.312-317
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    • 1992
  • The interaction of dioxouranium(VI) (uranyl) ion with nitrate ion has been studied by $^{17}O$ NMR spectroscopy. The $^{17}O$ resonance of uranyl oxygen atoms(uranyl oxygens hereafter) of $UO_2NO_3{^+}$ was at lower field than that of uranyl ion. The stability constants of $UO_2NO_3{^+}$ were obtained from the variation of $^{17}O$ chemical shifts with nitrate-ion concentration at 5, 15, 25, $35^{\circ}C$ and depend on the ionic strength. Thermodynamic parameters calculated from temperature dependence of the stability constants were as follows : ${\Delta}H=-(27.2{\pm}1.7)kJ\;mol^{-1}$ and ${\Delta}S=-(110{\pm}7)JK^{-1}mol^{-1}$. There was a linear relationship between the enthalpy and entropy for 1:1 complex formation of the uranyl ion with a variety of anionic ligands.

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XPS Studies for O1S Electrons of Ion Exchanged Zeolite X and Y (이온교환된 X형 및 Y형 제올라이트의 O1S 전자에 대한 X선 광전자분광학적 해석)

  • Kim, Myung-chul;Kim, Jong-Taik
    • Applied Chemistry for Engineering
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    • v.3 no.2
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    • pp.240-246
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    • 1992
  • The electronic structure of oxygen atom of cation-exchanged zeolite was investigated by utilizing X-ray photoelectron spectroscopy(XPS). The obtained $O_{1S}$ spectra of $Na^+-$, $Fe^{2+}-$ and $Fe^{3+}-$ exchanged zeolite X and Y were deconvoluted to demonstrate electronic binding energy of framework oxygens. There were 2-3 bands in each spectrum. The characteristics of separated band have been studied in terms of binding energy and relative area of $O_{1S}$ electron with respect to the exchanged cation. Those bands were assigned to the bridged oxygen in framework (band 1), cation bonded oxygen in cationic site (band 2) and oxygen in water coordinated to the cation (band 3) each other. The band 1 occupying the majority area of $O_{1S}$ spectrum was shifted to higher region on binding energy according to the decrease of Al content in zeolite.

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Interactions and Ionic Conductivities of Poly(epichlorohydrin) Graft Copolymer Electrolyte Membranes (Poly(epichlorohydrin) 가지형 공중합체 전해질막의 상호작용 및 이온 전도도)

  • Koh, Joo-Hwan;Lee, Kyung-Ju;Park, Jung-Tae;Ahn, Sung-Hoon;Kim, Jong-Hak
    • Membrane Journal
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    • v.20 no.3
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    • pp.203-209
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    • 2010
  • Amphiphilic graft copolymers based on poly(epichlorohydrine) (PECH) were synthesized using atom transfer radical polymerization (ATRP). Successful graft polymerization of poly(methyl methacrylate)(PMMA) and poly(butyl methacrylate) (PBMA) from PECH was confirmed by nuclear magnetic resonance ($^1H$ NMR) and FT-IR spectroscopy. Upon the introduction of KI or LiI to the graft copolymers, the ether stretching bands were shifted to a lower wavenumber due to coordinative interactions. Ionic conductivities of PECH-g-PBMA complexes were always higher than those of PECH-g-PMMA complexes, resulting from higher mobility of rubbery PBMA chains. The maximum ionic conductivity of $2.7{\times}10^{-5}\;S/cm$ was obtained at 10 wt% of KI for PECH-g-PBMA electrolytes.

An Experimental Evaluation of Clay Minerals to Remove Non-point Sources of Contaminants in the Urban Runoff (도시지역 지표우수의 비점오염원 제거를 위한 점토광물의 실험적 평가)

  • Song, Young-Woo;Rhee, Suk-Keun
    • International Journal of Highway Engineering
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    • v.14 no.1
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    • pp.55-61
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    • 2012
  • The ability of clay mineral to remove non-point sources such as SS, COD, T-N. T-P in the urban runoff has been tested to develop the porous filter material. The diameter of 3mm ball type filters were made of clay minerals for the tests. The experiments were carried out to measure the concentration of non-point sources of contaminants with flow rate of effluents. The test results show that clay filter has good response to remove SS, COD comparing to those of activated carbon filter. Also the performance of the clay filter to remove T-N and T-P is almost the same when using the activated carbon filter.

Catalytic Reactivity of Transition Metal (Pd, Ni) complexes with Aminophosphines; I. Carbon-Carbon coupling reactions (Aminophosphine류가 배위된 전이금속(Pd, Ni) 착물의 촉매반응; I. 탄소-탄소 짝지움 반응)

  • Jung, Maeng-Joon;Lee, Chul-Jae;Kim, Dong-Yeub
    • Journal of the Korean Society of Industry Convergence
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    • v.7 no.1
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    • pp.107-113
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    • 2004
  • Several transition metal complexes, [$M(L)X_2$](M=Pd(II), Ni(II); X=CI, Br) are prepared with aminophosphine ligands such as 1,2-bis{(diphenylphosphino)amino}ethane{$Ph_2PNHCH_2CH_2NHPPh_2$}($L_1$), 1,2-bis{(diphenylphosphino)amino}propane{$Ph_2PNHCH(CH_3)CH_2NHPPh_2$}($L_2$), trans-1,2-bis{(diphenylphosphino)amino}cyclohexane{$Ph_2PNHC_6H_{10}NHPPh_2$}($L_3$) and 1,2-bis{(diphenylphosphino)amino}benzene{$Ph_2PNHC_6H_4NHPPh_2$}($L_4$). The properties of these complexes are characterized by optical spectroscopic methods including UV/vis spectroscopy, CD, IR, $^1H$- and $^{31}P-NMR$ together with conductometer and elemental analysis. All complexes are stable under atmospheric environment. Catalytic reactivity for C-C coupling between [$M(L)X_2$] and Grignard reagents(RMgX; R=phenyl, propyl, buthyl) by thermolysis were investigated utilizing GC/mass, $^1H$- and $^{13}C-NMR$. When mol scale is 1:20 at [$Pd(L)Cl_2$] and Grignard reagents, the high catalytic activity for C-C coupling is apparent. The [$M(L)X_2$](X=Cl, Br) complexes which have strong bond at M-P exhibit high yields for C-C coupling reactions. When the central metal ion is Pd(II), the high catalytic activity for C-C coupling is apparent. The complex coordinated with Br shows higher catalytic activity for C-C coupling reactions compared to Cl.

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