• 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.

• Bulletin of the Korean Chemical Society
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• v.15 no.7
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• pp.549-553
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• 1994

The 2-(dimethylaminomethyl)thiophene (dmamt) complexes with copper(II) chloride and bromide were prepared and characterized by optical, EPR, XPS spectroscopies and magnetic susceptibility measurements. The low-energy absorption band above 850 nm and the relatively small EPR hyperfine coupling constant ($A_{//}{\simeq}$125 G) indicate the pseudotetrahedral site symmetry around copper(II) ion both in Cu(dmamt)$Cl_2$ and Cu(dmamt)$Br_2$ complexes. The higher satellite to main peak intensity of Cu $2P_{3/2}$ core electron binding energy in XPS spectra also supports the pseudotetrahedral geometry around the copper(II) ions having $CuNSX_2$ chromophores. The distortion from square-planar to pseudotetrahedral symmetry is likely to arise from the steric hindrance of the bulky dmamt ligand in the complex. Magnetic susceptibility study shows that these compounds follow Curie-Weiss law in the temperature range of 77-300 K with positive Weiss constant exhibiting the ferromagnetic interaction between copper(II) ions in solid state.

• Bulletin of the Korean Chemical Society
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• v.34 no.9
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• pp.2731-2736
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• 2013

We report a new tetrameric supramolecular Cu(II) complex ($Cu_4L_4$ = tetrakis(N,N'-bis(salicylidene)-2,2'-ethylenedianiline)Copper(II)) with a Schiff-base ligand ($H_2L$ = N,N'-bis (salicylaldimine)-1,2-ethylenediamine) containing two N,O-bidentate chelate groups. Though the copper sites of $Cu_4L_4$ are non-coupled, the complex exhibits a unsually high catecholase-like activity ($k_{cat}=935h^{-1}$) when the $Cu_4L_4$ solution is treated with 3,5-di-tert-butylcatechol (3,5-DTBC) at basic condition in the presence of air. Combined information obtained from UV-VIS and EPR measurements could lead the suggestion of the reaction pathway in which the substrate may bind to Cu(II) ions by anti-anti didentate bridging mode.

• Proceedings of the Korean Magnetic Resonance Society Conference
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• 2002.08a
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• pp.72-72
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• 2002

In most traditional sorption study in environmental conditions, experimental sorption data have been measured and interpreted by empirical ways such as partition coefficient and sorption isotherms. A mechanistic understanding of heavy metal interactions with various minerals (metal oxides, clay minerals) in aqueous medium is required to describe the behavior of radioactive metal ions in the environment. Various spectroscopic methods provide direct or indirect information on sorption mechanisms involved. We applied EPR (Electron Paramagnetic Resonance) spectroscopy to investigate the nature of metal ion sorption at water/mineral interfaces using Cu(II) as a spin probe. The major sorbed species and their motional state was identified by their EPR spectra. They showed distinct signals due to their strength of binding, local structure and motional state. The EPR results together with macroscopic sorption data show that sorption involved at least three different mechanisms depending on chemical environments (1).

• 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.

• Proceedings of the Petrological Society of Korea Conference
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• 2001.06a
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• pp.44-44
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• 2001

• Journal of the Korean Magnetics Society
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• v.5 no.5
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• pp.782-785
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• 1995

In this paper, $Mn^{2+}$ ion was doped in Y-Ba-Cu-O as an EPR probe. The following samples were prepared by conventional solid-state reaction method : $YBa_{2}Cu_{2.96}Mn_{0.04}O_{7-\delta}$ (MN-I), annealed $YBa_{2}Cu_{2.96}Mn_{0.04}O_{7-\delta}$ (AMN) and $YBa_{2}Cu_{2.94}Mn_{0.06}O_{7-\delta}$ (MN-II). AMN sample was obtained from MN-I by annealing for 1 hr under the Ar gas atmosphere at $600^{\circ}C$. X-band (~9.05 GHz) EPR spectra were measured from 103 K to room temperature by employing a JES-RE3X spectroscopy with a $TE_{0.11}$ cylindrical cavity and 100 kHz modulation frequency. In MN-I we have observed only the $Cu^{2+}$ signal. The fact that no $Mn^{2+}$ signal was observed, in spite of $Mn^{2+}$ being a very sensitive EPR probe, indicates that most likely isolated $Mn^{2+}$ ions don't exist in the MN-I sample. Most probably $Mn^{2+}$ ions in the MN-I sample interact antiferromagnetically and hence are EPR silent. The AMN spectra of at room temperature and 103 K indicate not only the $Cu^{2+}$ signal but also an extra signal, which increases with decreasing temperature. It is suggested that the extra signal originates from Mn ions that were antiferromagnetically coupled before the annealing process. In MN-II, from 103 K to room temperature, also, the extra signal was observed together with the $Cu^{2+}$ signal. The extra signal in MN-II, however, decreases with decreasing temperature and nearly disappears at 103 K. The signal originates from Mn ions in impurity phases that include $Mn^{2+}$ ions. We suppose that there exist at least two $Mn^{2+}$ doped phases in Y-Ba-Cu-O. The $Mn^{2+}$ signal of one phase is undectable at all temperature and that of another phase decreases with decreasing temperature and disappears around 103 K.

• Journal of the Mineralogical Society of Korea
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• v.17 no.1
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• pp.1-9
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• 2004

Copper(II) sorbed on kaolinite (KGa-lb) was studied using electron paramagnetic resonance (EPR) and extended X-ray absorption fine structure (EXAFS) spectroscopy. The sorbed copper(II) had an isotropic EPR signal with $g_{iso}\;=\;2.19$ at room temperature. At 77 K, the isotropic signal converted to an axially symmetric anisotropic signal with $g_{\$\mid$}\;=\;2.40,\;g_{\bot}\;=\;2.08,\;and\;A_{\$\mid$}\;=\;131\;G$. These EPR results suggest that the sorbed copper(II) forms an outer-sphere surface complex with a tetragonally distorted $CuO_{6}$ octahedral structure on the kaolinite. In the sorption measurement, the amount of sorbed copper increased with increasing pH of the solution. However, the intensity of the isotropic EPR line was not directly proportional to the amount of sorbed copper. This discrepancy was resolved by assuming the formation of a surface precipitate at higher pH that is invisible by EPR. The EXAFS data confirmed the existence of the surface precipitate. The best fit for the EXAFS of the sorbed copper showed that each copper on the kaolinite had 6.8 copper neighbors located $3.08\;{\AA}$ from it, in addition to the first shell oxygen neighbors, including 4 equatorial O at $1.96\;{\AA}$ and 2 axial O at $2.31\;{\AA}$. This work shows that the local environment of the copper sorbed on the kaolinite changes as a function of pH and surface loading, and that the EPR and EXAFS are useful in studying such changes.

• Bulletin of the Korean Chemical Society
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• v.11 no.2
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• pp.85-88
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• 1990

The electron paramagnetic resonance (EPR) spectrum of the copper (II) complex with the 2-methylamino-1-cyclo-pentene-1-dithiocarboxylate (acdc) anion, $Cu(N-CH_3acdc)_2$ has been studied in the diamagnetic host lattices afforded by the corresponding divalent nickel, zinc, cadmium and mercury complexes. EPR parameters of the complex support the exclusive use of sulfur atoms by the ligand in metal binding. A combination of host lattice structure and covalency effects can be account for the observed spin-Hamiltonian parameters.

• Journal of the Korean Chemical Society
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• v.55 no.2
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• pp.177-182
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• 2011

A diketo-type ligand was synthesized by the Knoevenagel condensation reaction of thiophene-2-aldehyde with acetylacetone, subsequently its transition metal complexes with Cu(II), Ni(II), and Co(II) chlorides were also prepared. All the complexes were characterized by various physico-chemical methods. The molar conductivity data reveals ionic nature for the complexes. The electronic spectrum and the EPR values suggest square planar geometry for the Cu(II) ion. Interaction of the Cu(II) complex with CTDNA (calf thymus DNA) was studied by absorption spectral method and cyclic voltammetry. The $k_{obs}$ values versus [DNA] gave a linear plot suggesting psuedo-first order reaction kinetics. The cyclic voltammogram of the Cu(II) complex reveals a quasi-reversible wave attributed to Cu(II)/Cu(I) redox couple for one electron transfer with $E_{1/2}$ values -0.240 V and -0.194 V. respectively. On addition of CTDNA, there is a shift in the $E_{1/2}$ values 168 mV and 18 mV respectively and decrease in Ep values. The shift in $E_{1/2}$ values in the presence of CTDNA suggests strong binding of Cu(II) complex to the CTDNA.