• Bulletin of the Korean Chemical Society
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• v.26 no.7
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• pp.1044-1050
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• 2005

The reaction of cis-[Cr([14]-decane)($OH_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = isothiocyanate ($NCS^-$), azide ($N3^-$) or chloroacetate(caa)} leads to a new cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ (1), cis-[Cr([14]-decane)($N_3)_2]ClO_4$ (2) or cis-[Cr([14]-decane)($caa)_2]ClO_4$ (3). These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two $NCS^-$anions are bonded to the chromium(III) ion via the Ndonor atom in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by 13$^{\circ}$ from the ideal value of 180$^{\circ}$ for a perfect octahedron. The bond angle N-Cr-N between the Cr(III) ion and the two nitrogen atoms of the isothiocyanate ligands is close to 90$^{\circ}$. The bond lengths of Cr-N between the chromium and $NCS^-$groups are 1.964(5) and 2.000(5) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 2073, 1344 and 1684 $cm^{-1}$ attributed to the $NCS^-$, ${N_3}^-$ and caa groups stretching vibrations, respectively.

• Bulletin of the Korean Chemical Society
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• v.30 no.11
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• pp.2754-2758
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• 2009

Three novel phosphorescent 2-phenylpyridine-based iridium(III) complexes, $[(ppy)_2Ir(P\^{}N)]PF6\;(1),\;[(dfppy)_2Ir(P\^{}N)]PF_6$ (2), and $[(dfmppy)_2 Ir(P\^{}N)]PF6$ (3), where $P\^{}N$ = 2-[(diphenylphosphino)methyl]pyridine (dppmp), were synthesized and characterized. The absorption, photoluminescence, cyclic voltammetry and thermal stability of the complexes were investigated. The complexes showed bright blue luminescences at wavelengths of 448 $\sim$ 500 nm at room temperature in $CHCl_3$ and revealed that the $\pi$-acceptor ability of the phosphorous atom in the ancillary dppmp ligand plays an important role in tuning emission color resulting in a blue-shift emission. The single crystal structure of $[(dfmppy))_2Ir(P\^N)]PF_6$ was determined using X-ray crystallography. The iridium metal center adopts a distorted octahedral structure coordinated to two dfmppy and one dppmp ligand, showing cis C-C and trans N-N chelate dispositions. There is a $\pi-\pi$ overlap between π electrons delocalized in the difluorophenyl rings.

• Bulletin of the Korean Chemical Society
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• v.34 no.1
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• pp.167-173
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• 2013

A series of highly efficient red phosphorescent heteroleptic iridium(III) complexes 1-6 containing two cyclometalating 2-(2,4-substitued phenyl)quinoxaline ligands and one chromophoric ancillary ligand were synthesized: (pqx)$_2Ir$(mprz) (1), (dmpqx)$_2Ir$(mprz) (2), (dfpqx)$_2Ir$(mprz) (3), (pqx)$_2Ir$(prz) (4), (dmpqx)$_2Ir$(prz) (5), (dfpqx)$_2Ir$(prz) (6), where pqx = 2-phenylquinoxaline, dfpqx = 2-(2,4-diflourophenyl)quinoxaline, dmpqx = 2-(2,4-dimethoxyphenyl)quinoxaline, prz = 2-pyrazinecarboxylate and mprz = 5-methyl-2-pyrazinecarboxylate. The absorption, emission, electrochemical and thermal properties of the complexes were evaluated for potential applications to organic light-emitting diodes (OLEDs). The structure of complex 2 was also determined by single-crystal X-ray diffraction analysis. Complex 2 exhibited distorted octahedral geometry around the iridium metal ion, for which 2-(2,4-dimethoxyphenyl)quinoxaline N atoms and C atoms of orthometalated phenyl groups are located at the mutual trans and cis-positions, respectively. The emission spectra of the complexes are governed largely by the nature of the cyclometalating ligand, and the phosphorescent peak wavelengths can be tuned from 588 to 630 nm with high quantum efficiencies of 0.64 to 0.86. Cyclic voltammetry revealed irreversible metal-centered oxidation with potentials in the range of 1.16 to 1.89 V as well as two quasi-reversible reduction waves with potentials ranging from -0.94 to -1.54 V due to the sequential addition of two electrons to the more electron-accepting heterocyclic portion of two distinctive cyclometalated C^N ligands.

• Journal of the Korean Magnetic Resonance Society
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• v.9 no.2
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• pp.138-154
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• 2005

Vanadium-incorporated aluminophosphate molecular sieve $VO^{2+}-SAPO-5$ was studied by electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopies to determine the vanadium structure and interaction with various adsorbate molecules. It was found that the main species at low concentration of vanadium is a monomeric vanadium units in square pyramidal or distorted octahedral coordination, both in oxidation state (IV) for the calcined hydrated material and in oxidation state (V) for the calcined material. After calcinations in $O_2$ and exposure to moisture, only species A is observed with reduced intensities. It is suggested as a $VO(H_2O)_3^{2+}$ complex coordinated to two framework oxygen bonded aluminum. When calcined, hydrated $VO^{2+}-}SAPO-5$ is dehydrated at elevated temperature, a species loses its water ligands and transforms to $VO^{2+}$ ions coordinated to two framework oxygens (species B). Species B reduces its intensity, significantly after treatment with $O_2\;at\;600^{\circ}C$ for 5 h, thus suggesting oxidation of $V^{4+}\;to\;V^{5+}$. When dehydrated $VO^{2+}-SAPO-5$ contacts with $D_2O$ at room temperature, the EPR signal of species A is observed. Thus species assumed as a $VO^{2+}(O_f)_2(D_2O)_3$, by considering two framework oxygens. Adsorption of deuterated ethanol, propanol on dehydrated $VO^{2+}_{-}SAPO-5$ result in another new vanadium species E and F, respectively, which are identified as a $VO^{2+}-(CH_3CH_2OD)_3,\;VO^{2+}-(CH_3CH_2CH_2OD)_2$ complex. When deuterated benzene is adsorbed on dehydrated $VO^{2+}-SAPO-5$, another new vanadium species G, identified as a $VO^{2+}-(C_6D_6)$ is observed. Possible coordination geometries of these various complexes are discussed.

• Journal of the Korean Chemical Society
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• v.34 no.5
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• pp.438-444
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• 1990

Observed rate constants (k$_{obs.}$) for Hg$^{2+}$-catalysed aquation of cis-[Co(en)$_2$(OH$_2$)Cl]$^{2+}$, [Co(NH$_3$)$_5$Cl]$^{2+}$, cis-[Co(NH$_3$)$_4$(OH$_2$)Cl]$^{2+}$, and [Co(NH$_2$CH$_3$)$_5$Cl]$^{2+}$ were measured at various concentrations of Hg$^{2+}$. The k$_{obs.}$ was increased with increasing the concentrations of Hg$^{2+}$. The k$_{obs.}$ were related to mechanistically derived rate constants by the relationship; Rate = k$_2$K[complex][Hg$^{2+}$]. Various mixed aqueous-organic solvent have been successfully employed for Hg$^{2+}$-catalysed aquation of octahedral myetal complexes. From the slope of the plot of log k againt Y (solvent ionizing power), the mechanism on the aquation of Co(Ⅲ) complexes by Hg$^{2+}$ has been suggested to be I$_d$-mechanism. The change in a rate on aquation of each Co(Ⅲ) complex was related to the ligand field parameters (${\Delta}$), for Co(Ⅲ) complexes.

• Analytical Science and Technology
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• v.12 no.5
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• pp.421-427
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• 1999

Two shapes of crystals have been isolated by the interdiffusion of $Co(NCS)_2$ dissolved in methanol with 1,2-bis(2,2'-bipyridyl-6-yl)ethane (bbpe) dissolved in chloroform. The two crystals have been elucidated as $trans-Co^{II}(NCS)_2(bbpe)$ and $trans-Co^{II}(NCS)_2(bbpe){\cdot}2CHCl_3$, by X-ray crystallography, elemental analysis, IR, and thermal analysis. The two molecular structures are very similar except for the absence or presence of chloroform solvate molecules. The bbpe ligand coordinates to the cobalt(II) ion in an open-ended tetradentate mode, resulting in discrete mononuclear cobalt(II) complex. The cobalt atom adopts a typical octahedral arrangement with six nitrogen donating atoms with two NCS groups in trans positions. A significant solid-to-solid phase transition occurs presumably due to the change of conformationally flexible bbpe ligand. The formation of both crystals oeeurs in a successive two-step process, the formation of $trans-Co^{II}(NCS)_2(bbpe)$ and its transformation into $trans-Co^{II}(NCS)_2(bbpe){\cdot}2CHCl_3$. The thermal stability and favorable formation of the solvate crystals may be ascribed to the interaction between S atom of NCS group and Cl of chloroform.

• Journal of the Korean Chemical Society
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• v.36 no.6
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• pp.872-878
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• 1992

Some vanadium(III) complexes have been prepared by the reaction of VCl3${\cdot}$3MeCN with ligands and characterized by elemental analysis, 1H-NMR, infrared and UV-Visible spectroscopy. 3,5-lutidine(lutd), 8-hydroxyquinoline(oxine), 1,2-phenylenediamine(phda), ethylenediamine(en), and sym-diphenylethylenediamine(dpen) were chosen as coordinating ligands. ${\nu}$(V-Cl) of lutidine complex occurs at 418 $cm^{-1}$ and the other complexes (oxine, phda, en, dpen) occur at 337∼347 $cm^{-1}$. The value of ${\nu}$(V-Cl) indicates that the former complex has trigonal bipyramid structure and the latter complexes have octahedral structure. The ${\nu}$(C${\equiv}$N) of acetonitrile in oxine and phda complexes are characteristically shifted to about 70 $cm^{-1}$ higher frequency compared with that of free ligand (2260 $cm^{-1}$). The ${\delta}$(C${\equiv}$N) is also shifted to about 60 $cm^{-1}$ higher frequency compared with that of free ligand (377 $cm^{-1}$). Finally each vanadium(III) complex showed the following formulation; [$VCl_3(lutd)_2$], [$VCl(oxine)_2$MeCN]$Cl_2$, [$VCl(phda)_2$MeCN]$Cl_2$, [$VCl_2(en)_2$]Cl, [$VCl_2(dpen)_2$]Cl.

• Journal of the Korean Chemical Society
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• v.55 no.4
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• pp.603-611
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• 2011

Ethoxylacetyl oxime ligands [HL, (1) and $H_2L^1$, (3)] react with copper(II) acetate monohydrate yield octahedral and square planar complexes, respectively. The complexes have been postulated due to elemental analyses, IR, UVVis. spectra, magnetic susceptibility, conductivity and ESR spectra. Molar conductance of the complexes in DMF indicates a non-ionic character. The ESR spectra of [$(L)_2Cu(H_2O)_2$], (2) complex at room temperature and 77K are characteristic of an axial symmetry ($d_{x2-y2}$) with covalent bond character and have a large line width typical of dipolar interactions. However, [$(L^1)Cu$], (4) complex in the solid state showed spectra of marked broadening and loss of hyperfine splitting confirming spinexchange interactions between the copper(II) sites. The spectrum of the doped copper(II) complex at room temperature showed super-hyperfine splitting from coordinated nitrogen atoms and it has an axial type ($d_{x2-y2}$) with covalent bond character and an essentially square-planar arrangement around the copper(II) ion. The spectrum of [$(L^1)Cu$], (4) in frozen methanol at 77K was characteristic of the triplet state of a dimer species and the distance found between the two copper(II) centers was calculated and is equal to 4.8 ${\AA}$.

• Proceedings of the Korean Vacuum Society Conference
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• 2015.08a
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• pp.230.2-230.2
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• 2015

Nanoparticles of magnesium ferrite are used as a heterogeneous catalyst, humidity sensor, oxygen sensor and cure of local hyperthermia. These applications usually utilize the magnetic behavior of these nanoparticles. Moreover, magnetic properties of nanoferrites exhibit rather complex behavior compared to bulk ferrite. The magnetic properties of ferrites are complicated by spins at vortices, surface spins. Reports till date indicate strong dependency on the structural parameters, oxidation state of metal ions and their presence in octahedral and tetrahedral environment. Thus we have carried out investigation on magnesium ferrite nanoparticles in order to study coordination, oxidation state and structural distortion. For present work, magnesium ferrite nanoparticles were synthesized using nitrates of metal ions and citric acid. Fe L-edge spectra measured for these nanoparticles shows attributes of $Fe^{3+}$ in high spin state. Moreover O K-edge spectra for these nanoparticles exhibit spectral features that arises due to unoccupied states of O 2p character hybridized with metal ions. Mg K-edge spectra shows spectral features at 1304, 1307, 1311 and 1324 eV for nanoparticles obtained after annealing at 400, 500, 600, 800, 1000, and $1200^{\circ}C$. Apart from this, spectra for precursor and nanoparticles obtained at $300^{\circ}C$ exhibit a broad peak centered around 1305 eV. A shoulde rlike structure is present at 1301 eV in spectra for precursor. This feature does not appear after annealing. After annealing a small kink appear at ~1297 eV in Mg K-edge spectra for all nanoparticles. This indicates changes in local electronic structure during annealing of precursor. Observed behavior of change in local electronic structure will be discussed on the basis of existing theories.

• Journal of the Korean Applied Science and Technology
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• v.22 no.3
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• pp.204-211
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• 2005

The structure of nitrogen adsorption complex of fully dehydrated $Cd^{2+}$ ion exchanged zeolite-X, $|Cd_{46}(N)_{18}|[Si_{100}Al_{92}O_{384}]$, was determined in the cubic space group $Fd\overline{3}$ at 21(1) $^{\circ}C$ [a = 24.863(4) ] by single crystal X-ray diffraction analysis. The crystal was prepared by ion exchange in a flowing steam of 0.05 M aqueous solution $Cd(NO_3)_2$ : $Cd(O_2CCH_3)_2$ = 1:1 for five days, followed by dehydration at $500^{\circ}C$ and $2{\times}10^{-6}$ Tor. for two days, and exposured to 100 Tor. zeolitically dry nitrogen gas at 21(1) $^{\circ}C$. The structure was determined in atmosphere, and was refined within $F_0$ > $4{\sigma}(F_0)$ using reflection for which the final error can appear in indices $R_1$ = 0.097 and $wR_2$ = 0.150. In this structure, $Cd^{2+}$ ions occupied four crystallographic sites. Nine $Cd^{2+}$ ions filled the octahedral site I at the centers of hexagonal prisms (Cd-O = 2.452(16) ${\AA}$). Eight $Cd^{2+}$ ions filled site I' (Cd-O = 2.324(19) ${\AA}$). The remaining 29 $Cd^{2+}$ ions are found at two nonequivalent sites II (in the supercages) with occupancy of 11 and 18 ions. Each of these $Cd^{2+}$ ions coordinated to three framework oxygens, either at 2.159(15) or 2.147(14) ${\AA}$, respectively. Eighteen nitrogen molecules were adsorbed per unit cell and three per supercage.