• Title/Summary/Keyword: Crystal EPR

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Structural Analysis and Single-Crystal EPR Study of Dimeric Cu(I) Complex with TTF Derivative

  • Kwon, Sun-Young;Seo, Young-Joo;Lee, Yang-Joo;Noh, Dong-Youn;Lee, Hong-In
    • Journal of the Korean Magnetic Resonance Society
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    • v.8 no.2
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    • pp.86-95
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    • 2004
  • A Cu(I) complex with an asymmetric TTF derivative (CET-EDTTTF) is prepared from the slow-diffusion method using CET-EDTTTF and Cu(I)Br solutions and characterized by X-ray crystallography and EPR spectroscopy. Structural analysis shows Cu(I) ions are tetrahedrally coordinated to two bridging bromides, one terminal bromide, and one S atom from CET-EDTTTF. Detailed geometrical and EPR analysis identified that the dimmer molecule contains [Cu$_2Br_4]^{2-}$ anion between two [CET-EDTTTF]$^+$ radical cations. Single-crystal EPR investigation of the complex reveals that the ganisotropy is unusually big, compared to those of the previously reported TTF+ cation radicals, implying that there is significant contribution of the Cu d-orbital to the HOMO of the complex.

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EPR Lineshape and g-Factor of the Single Crystal $Mn_xSi_{1-x}$

  • Son, Phil-Kook;Hwang, Young-Hun;Heo, Kyong-Chan;Kim, Hung-Cheol;Ok, Chi-Il;Um, Young-Ho;Kim, Jang-Whan
    • Journal of the Korean Magnetic Resonance Society
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    • v.8 no.1
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    • pp.47-54
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    • 2004
  • We have measured the linewidth and g-factor of EPR signals of the single crystal Mn$_{x}$Si$_{1-x}$ as a function of Mn-composition (0.4$\leq$x$\leq$0.9). We have investigated the linewidth of Mn$_{0.49}$Si$_{0.51}$ as a function of temperature (100 $\leq$ T $\leq$ 300 K). From these results EPR linewidth equation could be fitted for experimental data of EPR linewidth. This type of equation is similar to the shape of EPR linewidth of DMS (dulite magnetic semiconductor).or).r).

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Detection of gamma irradiated South Sea cultured pearls (감마선 조사된 남양진주의 검지)

  • Choi, Hyun-Min;Lee, Bo-Hyun;Kim, Young-Chool
    • Journal of the Korean Crystal Growth and Crystal Technology
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    • v.22 no.1
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    • pp.36-41
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    • 2012
  • We have been performed on $Co^{60}$ ${\gamma}$-ray irradiation of South Sea cultured pearls, with the absorbed dose of 0.1~100 kGy at room temperature. In addition, it was investigated electron paramagnetic resonance (EPR) and amino acid analysis (AAA) for detection of Gamma irradiated South Sea cultured pearls. It was observed that the irradiated South Sea cultured pearls revealed additional free radical peak such as $CO_2^-$, at a g-factor of $2.001{\pm}0.002$ in EPR spectra. From the amino acid analysis (AAA), it was shown that some of amino acid in the protein of the nacre destroyed after ${\gamma}$-ray; glutamic acid residue by 11.43 %, alanine by 3.11 %, and histidine by 43.75 %. It was useful to detect the irradiated South Sea cultured pearls by EPR measurement in our study.

Temperature Dependence of Mn2+ Paramagnetic Ion in a Stoichiometric LiNbO3 Single Crystal

  • Yeom, Tae Ho;Lee, Soo Hyung
    • Journal of Magnetics
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    • v.18 no.3
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    • pp.221-224
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    • 2013
  • Electron paramagnetic resonance (EPR) spectra of $Mn^{2+}$ impurity ion in Stoichiometric $LiNbO_3$ single crystal (SLN) was investigated with an X-band EPR spectrometer in the temperature range of 3 K~296 K. The intensity of EPR spectrum of $Mn^{2+}$ ion was increased to 20 K and decreased again below 20 K as the temperature decreases. The zero-field splitting parameter D decreased as the temperature increases. It was suggested that $Mn^{2+}$ ion substitute for $Nb^{5+}$ ion instead of $Li^+$ ion. No changes for hyperfine interaction of $Mn^{2+}$ ion was obtained in the temperature range of 3 K~296 K.

Single Crystal EPR Spectra of $K_{12}[As_2W_18O_{66}Cu_3(H_2O)_2]{\cdot}11H_2O$, a Copper(II) Trimer

  • Jo, Yeong Hwan;So, Hyeon Su
    • Bulletin of the Korean Chemical Society
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    • v.16 no.3
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    • pp.243-248
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    • 1995
  • Single crystal EPR spectra of K12[As2W18O66Cu3(H2O)2]${\cdot}$11H2O exhibit an orientation-dependent fine structure of an S = 3/2 system which is accounted for by the exchange and magnetic dipole interactions among the three Cu2+ ions. The hyperfine structure and the lines from the S = 1/2 manifolds have not been observed. The isotropic exchange parameters determined from the magnetic susceptibility data at 5-300 K are J1 = J2 =-7.8 cm-1. The magnitude of J values suggests that the unpaired electrons on three Cu2+ ions interact through a sequence of six bonds involving two tungsten atoms and three oxygen atoms. The Cu-Cu distance, 4.37 $\AA$, determined from the EPR spectra is considerably smaller than the value from the X-ray crystal structure determination, 4.76 $\pm$ 0.03 $\AA$, indicating that the point-dipole model underestimates the dipolar interaction.

Electron Magnetic Resonance of Eu2+ in SrCl2:Eu Single Crystal

  • Lee, Soo Hyung;Yeom, Tae Ho;Kim, Sung-Hwan
    • Journal of Magnetics
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    • v.17 no.4
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    • pp.251-254
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    • 2012
  • The electron paramagnetic resonance (EPR) of the $Eu^{2+}$ ion in $SrCl_2$:Eu single crystal has been investigated using an X-band spectrometer. The angular dependence of magnetic resonance positions for the $Eu^{2+}$ impurity ion in the crystallographic aa-plane is analyzed with effective spin-Hamiltonian. The EPR spectra of the isolated $Eu^{2+}$ center merged to each other. The hyperfine splitting of the isolated $Eu^{2+}$ center due to the $^{151}Eu$ nucleus is approximately 35 G. Three kinds of $Eu^{2+}$ centers except the isolated $Eu^{2+}$ center, $Eu^{2+}$ pairs, $Eu^{2+}$ triples, and other $Eu^{2+}$ clusters, are split from the fitting of the integrated experimental spectrum with the Gaussian curve. The calculated spectroscopic splitting parameters of the $Eu^{2+}$ pairs, $Eu^{2+}$ triples, and other $Eu^{2+}$ clusters in $SrCl_2$:Eu crystal are $g_1$ = 2.06, $g_2$ = 1.94, and $g_3$ = 1.93, respectively.

Electronic Structure of [NiS4]- Investigated by Single-Crystal EPR and Density Functional Theory

  • Min, Su-Young;Noh, Dong-Youn;Choi, Cheol-Ho;Lee, Hong-In
    • Journal of the Korean Magnetic Resonance Society
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    • v.16 no.1
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    • pp.78-90
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    • 2012
  • To understand the electronic structure of $[NiS_4]^-$ complex ions, two complexes with such $[NiS_4]^-$ core, $FcCH=CHPymCH_3[Ni(dmit)_2]$ (Pym = pyridinium, $dmit^{2-}$ = 2-thioxo-1,3-dithiole-4,5-dithiolate) and $FcCH=CHPymCH_3[Ni(dddt)_2]{\cdot}{\frac{1}{2}}H_2O$ ($dddt^{2-}=5,6-dihydro-1,4-dithiin-2,3-dithiolato$), were synthesized to be characterized by X-ray crystallography, single crystal electron paramagnetic resonance (EPR) and density functional theory (DFT) calculation. Powder EPR spectra show narrow g-anisotropy but the anisotropy is bigger in $[Ni(dmit)_2]^-$ than in $[Ni(dddt)_2]^-$, indicating bigger spin density in Ni(III) d-orbital of $[Ni(dmit)_2]^-$ than in $[Ni(dddt)_2]^-$, which is consistent to DFT results. EPR studies of the crystals of the complexes surprisingly suggest that the $g_y$-axis of $[Ni(dddt)_2]^-$ is approximately on or perpendicular to the $[NiS_4]^-$ plane while the $g_y$-axis of $[Ni(dmit)_2]^-$ is on the plane, though DFT study of the complexes of this study and previously reported $[NiS_4]^-$ complexes indicate that the $g_y$-axis is on the $[NiS_4]^-$ plane.

Determination of a Weak Exchange Interaction in Magnetically Coupled Cluster System by EPR Singlet-Triplet Transition Lines

  • Cho, Young-Hwan;Hyunsoo So
    • Proceedings of the Korean Magnetic Resonance Society Conference
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    • 2002.08a
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    • pp.70-71
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    • 2002
  • Exchange-coupled cluster of transition-metal ions are relevant to many different scientific areas, ranging from chemistry to solid-state physics, biology, material science and has been the subject of much research in recent years(1,2). Single crystal EPR spectroscopy works as a very effective tool for the measurement of J values for small exchange interactions. This makes EPR technique very suitable for detection of weak exchange coupling transmitted over long distances via extended atomic and melecular bridges. Large polyoxometallates (3) may provide ideal structural environments for the study of interactions between paramagnetic ions. The detailed nature of magnetic interaction (positive sign and magnitude of J~0.006 $cm^{-1}$ /) was clearly determined for di-copper(II) system by single crystal EPR spectroscopy (4). The single-triplet (S-T) transitions are forbidden by different symmetries of the wave functions. However, when the singlet ground state is mixed into triplet states, the S-T transitions can be allowed and observed as weak lines. These weak S-T lines are positioned symmetrically with respect to the main transitions in the distance equals to 2J from the center of the spectrum. This lines allow one to determine the J-value with very high accuracy when │J│ < hv 0.32 $cm^{-1}$ /. Unfortunately, the S-T transitions in the single crystal were detected by EPR method only in a few complexes until now. We have measured single-triplet transition lines for several magnetically coupled cluster systems and determined their J values accurately. The temperature dependency of J was studied by monitoring the changes in S-T.

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Hydrothermal Synthesis, Crystal Structure and EPR Property of Tetranuclear Copper(II) Cluster [Cu4OCl6(C14H12N2)4]

  • Jian, Fang-Fang;Zhao, Pu-Su;Wang, Huan-Xiang;Lu, Lu-De
    • Bulletin of the Korean Chemical Society
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    • v.25 no.5
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    • pp.673-675
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    • 2004
  • The tetranuclear copper(II) cluster compound $[Cu_4OCl_6(C_{14}H_{12}N_2)_4]$ has been synthesized by hydrothermal reaction and studied by X-ray diffraction. The four copper(II) atoms locate four capsheaves of a tetrahedral skeletal structure and a oxygen atom as interstitial atom occupies the center position of the same tetrahedron, and each edge of the Cu-Cu tetrahedron is bridged by one ${\mu}_2$-Cl anion. The copper atom possesses slightly distorted trigonal bipyramidal geometry with three ${\mu}_2$-Cl atoms in equatorial position and the interstitial O atom and one N atom from 3-benzyl-benzimidazole ligand occupying axial position. The Cu-Cu distances are in the range of 3.0986-3.1162 ${\AA}$. The EPR spectrum suggested that the copper(II) ground state $d_{x2-y2}$ and the coordination geometry was trigonal bipyramidal.