• Title/Summary/Keyword: Paramagnetic

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$^1H$ NMR Study of 4-Aminopyrimidine Coordinated to the Paramagnetic Undecatung-stocobalto(Ⅱ)silicate Anion: Rates of Internal Rotation of the Amine Group

  • 김병안;소현수
    • Bulletin of the Korean Chemical Society
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    • v.20 no.10
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    • pp.1149-1152
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    • 1999
  • 1H NMR spectrum of a DMF-d7 solution containing 4-aminopyrimidine and [SiW11CoIIO39]6- (SiW11Co) shows separate peaks from two linkage isomers, a and b, in which N(1) and N(3) of the pyrimidine ring are coordinated to SiW11Co, respectively. The signal from the amine group in the isomer a exhibits temperature dependence that is characteristic of a two-site exchange problem. Rates of internal rotation of the amine group were determined by simulating the NMR spectra at 5-35℃. The amine group of free 4-aminopyrimidine also shows temperature-dependent spectra at lower temperatures; rates of internal rotation at (-25)-25℃ were determined. The internal rotation of the amine group in the complex is much slower than that for free 4-aminopyrimidine, indicating that π-character of the C-N bond increases on coordination to SiW11Co. The amine group in the isomer b does not show such behavior. It is probable that hydrogen bonding between N-H and a bridging oxygen atom of SiW11Co prevents it from rotating at low temperatures.

Paramagnetic Inversion of the Sign of the Interference Contribution to the Transverse Relaxation of the Imido Protons of the Coordinated Imidazoles in the Uniformly $^{15}N$ Labeled Cytochrome $c_3$

  • Andre Kim;Jeong, In Cheol;Sim, Yun Bo;Gang, Sin Won;Park, Jang Su
    • Bulletin of the Korean Chemical Society
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    • v.22 no.11
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    • pp.1197-1201
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    • 2001
  • In the spectrum of uniformly 15N labeled cytochrome c3, the relative linewidths of the doublet peaks of the 15N-coupled imido proton of the coordinated imidazole group were reversed on oxidation. This inversion was explained by the interference relaxation process between the electron-proton dipolar and 15N-1H dipolear interactions. The inversion can be used to assign the imido protons of the coordinated imidazole groups in heme proteins.

Preparation and EPR Characteristics of $ZnGa_2O_4$ : Mn Phosphor

  • 정하균;박도순;박윤창
    • Bulletin of the Korean Chemical Society
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    • v.19 no.12
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    • pp.1320-1325
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    • 1998
  • ZnGa2O4: Mn phosphors were prepared by a new chemical process, and their photoluminescence and electron paramagnetic resonance characteristics were investigated. The chemical method showed a low temperature formation of phosphors and a rod-type shape of particles. The strong ultraviolet emission was observed in the undoped ZnGa2O4 phosphor, while strong green emission in the Mn2+-activated ZnGa2O4 phosphor. The green emission intensity of the phosphor prepared by the chemical method was much stronger than that prepared by the conventional method. This difference with preparation methods was interpreted as due to the difference in the distribution of Mn2+ in the host lattice. From EPR results, it was explained that the line intensity of the undoped ZnGa2O4 is associated with the electrical conductivity of this material and the concentration quenching of green luminescence of ZnGa2O4: Mn at higher Mn2+ concentration is attributed to the coupling by exchange interaction between Mn2+ ions.

Preparation and Photoluminescence Properties of the ZnGa₂O₄: Mn Phosphor by Polymerized Complex Precursor

  • 조두환;정하균;석상일;박도순
    • Bulletin of the Korean Chemical Society
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    • v.18 no.6
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    • pp.608-612
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    • 1997
  • The preparation and photoluminescence properties of $ZnGa_2O_4$ : Mn phosphor are presented. Under 254 nm excitation $Zn_1-_xMn_xGa_2O_4$ exhibits the green emission band at 506 nm wavelength and maximum intensity where x=0.005. The manganese activated $ZnGa_2O_4$ phosphor prepared by the polymerized complex method shows a remarkable increase in the emission intensity and is smaller particle size than that prepared by conventional method. Also, electron paramagnetic resonance study on $ZnGa_2O_4$ : Mn powders indicates that the increase in emission intensity after firing treatment in mild hydrogen reducing atmosphere is due to the conversion of the higher valent manganese to $Mn^{2+}$.

The Pseudocontact Shift for a $3d^9$ System in a Strong Crystal Field Environment of Tetragonally Distorted Tetrahedral Symmetry

  • Kim, Dong-Hee;Lee, Kee-Hag
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.618-625
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    • 1991
  • A general expression adopting a nonmultipole expansion method is derived for pseudocontact contribution to the NMR chemical shift arising from the electron orbital angular momentum and electron spin dipolar-nuclear spin angular momentum interaction of $3d^9$ system in a strong crystal field of tetragonally distorted tetrahedral symmetry. From this expression all the multipolar term are determined and the exact solution of ${\Delta}$B/B(ppm) is compared with the multipolar term. The $1/R^5$ term in the multipolar terms contributes dominantly to the NMR chemical shift but the other terms are certainly significant except that of the <111> axis. In addition, an analysis of the temperature dependence of the NMR chemical shift further illustrates that considerable care must be taken in interpeting NMR results in paramagnetic system.

Syntheses and Reactivites with Olefins of Ruthenium(IV) Oxo/Ruthenium(II)-Aqua Complexes that Contain 2,6-Bis(N-pyrazolylpyridine)

  • Jo, Du-Hwan;Yeo, Hwan-Jin
    • Bulletin of the Korean Chemical Society
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    • v.14 no.6
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    • pp.682-686
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    • 1993
  • The syntheses and reactivities with olefins of $[Ru^{II}(L_3)(L_2)OH_2]^{2+}$ $[L_3$= 2,6-bis(N-pyrazolyl)pyridine(bpp), 2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine $(Me_4bpp);\;L_2$= 2,2'-bipyridine(bpy), 4,4'-dimethyl-2,2'-bipyridine $(Me_2bpy)$] are described. Their spectral and redox properties in aqueous solution were investigated. Evidence for each one electron redox process for the $Ru^{IV}-Ru^{III}$ and $Ru^{III}-Ru^{II}$ couples has been obtained. Oxidation of $[Ru^{II}(bpp)(bpy)OH_2]^{2+}$ with $Ce^{IV}$ gave $[Ru^{IV}(bpp)(bpy)O]^{2+}$. The $[Ru^{IV}$= 0 complex is paramagnetic $({\mu}_{eff}=2.82)$ and the complexes $[Ru(L_3)(L_2)OH_2]^{2+}$ are robust catalysts for the oxidation of styrene, cyclohexene, and cyclooctene with cooxidant such as NaOCl. Product distributions and selectivities are discussed by varying the number of the substituted-methyl group in the ring.

ANOMALOUS HALL EFFECT IN AMORPHOUS $Fe_{0.33}Zr_{0.67}$ ALLOY

  • Rhie, K.;Naugle, D.G.
    • Journal of the Korean Magnetics Society
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    • v.5 no.6
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    • pp.952-955
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    • 1995
  • It is well kown that the side-jump effect, originated from the spin-orbit scatterring of the transport electrons at the site of spin-orbit scatterers, is the reason for the anomalus Hall resistivity which is proportional to the magnetization. Our recent magnetization study implied that abundant ferromagnetic Fe clusters made of for Fe ions dominate the temperature and field dependence of magnetization at high field and low temperature regime for a paramagnetic $Fe_{0.33}Zr_{0.67}$ alloy. We measured the Hall resistivity of this alloy and observed that the Hall resistivity followed the M-H cure at low temperature, and the Hall coefficients at moderate temperatures were proportional to the magnetic susceptibility. We explain the behavior of Hall resistivity with the change of field and temperature in terms of side-jump effect.

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STUDY OF MAGNETISM IN THE LAYERED TRANSITION METAL COMPOUND ${(C_{n}H_{2n+1}NH_{3})}_{2}CuCl_{4}\;(n=10,\;14)$

  • Lee, C.H.;Lee, K.W.;Lee, Cheol-Eui;Kang, J.K.
    • Journal of the Korean Magnetics Society
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    • v.5 no.5
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    • pp.358-361
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    • 1995
  • We have investigated the quasi-two-dimensional magnetism for the layered transition metal compound (C/sub n/H/sub 2n+1/NH/sub 3/)/sub 2/CuCl/sub 4/ (n=10, 14) in the high temperature regions by means of EPR (Electron Paramagnetic Resonance) and SQUID measurements. As a result, the magnetic transitions were reflected in the EPR linewidths and the magnetic suceptibilities in a sensitive manner. Fluctuations of the magnetic susceptibility and a similar variation of the .DELTA. g =(g/sub .parallel. -/g/sub .perp. /)g/sub .parallel. / value were also observed around the structural phase transition temperatures.

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Magnetic NDE for Sensitization of Inconel 600 Alloy

  • Kikuchi, Hiroaki;Sumimoto, Takaki;Kamada, Yasuhiro;Kobayashi, Satoru
    • Journal of Magnetics
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    • v.18 no.3
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    • pp.348-351
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    • 2013
  • Inconel 600 alloy, Ni base alloy, is widely used for steam generator tubings where sensitization occurs at grain boundaries and sensitization will induce tubing failures. This alloy has usually paramagnetic property, however, it transforms into ferromagnetic property along grain boundaries when sensitization occurs: this means NDE using magnetism for sensitization is possible. Therefore, in this study, Inconel 600 alloys were heat treated at 873 K from 0 to 400 hours so as to generate sensitization and their magnetic properties were investigated in detail. The saturation and the residual magnetization increase with increasing heat treatment time and take a maximum. On the other hand, the coercive force decreases with the increase in time of heat treatment. We confirmed that characteristics at only grain boundaries change into ferromagnetic phase by a MFM observation. As a trial for industrial application, heat treated Inconel 600 alloy was scanned by a magnetic field sensor, and the variations in magnetization were obtained nondestructively. The results indicate a feasibility of magnetic NDE for sensitization of Inconel 600 alloy.