• Title/Summary/Keyword: Octahedral structure

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X-ray absorption spectroscopic study of MgFe2O4 nanoparticles

  • Singh, Jitendra Pal;Lim, Weon Cheol;Song, Jonghan;Kim, Joon Kon;Chae, Keun Hwa
    • 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.

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Syntheses and Characterization of Cr(III)-Hydrogensalicylato and -Hydroxonitrophenolato Tetraaza Macrocyclic Complexes

  • Byun, Jong-Chul;Yoon, Chang-Hoon;Mun, Dae-Hun;Kim, Ki-Ju;Park, Yu-Chul
    • Bulletin of the Korean Chemical Society
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    • v.27 no.5
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    • pp.687-693
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    • 2006
  • Chromium(III) complexes, cis-[Cr([14]-decane)$(HOC _6H _4COO) _2$]$ClO _4$ I and cis-[Cr([14]-decane)(OH) $(OC _6H _4NO _2)$]$ClO _4{\cdot}H _2O$ II ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) are synthesized and structurally characterized by a combination of elemental analysis, conductivity, IR and VIS spectroscopy, and X-ray crystallography. The complexes crystallizes in the monoclinic space groups, $C2 _1$/a in I and $P2 _1$/n in II. Analysis of the crystal structure of complex I reveals that central chromium(III) ion has a distorted octahedral coordination environment and two hydrogensalicylato ligands are unidentate to the chromium(III) ion via the carboxyl groups in the cis-position. For monomeric complex I the hydrogensalicylato coordination geometry is as follows: Cr-O(average) = 1.984(3) $\AA$;Cr-N range = 2.105(3)-2.141(4) $\AA$;C(24)-O(4) = 1.286(5) $\AA$;N(2)-Cr-N(4) (equatorial position) = 96.97(15)${^{\circ}}$; N(1)-Cr-N(3) (axial position) = 168.27(15)${^{\circ}}$; O(1)-Cr-O(4) = 85.70(13)${^{\circ}}$. The crystal structure of II has indicated that chromium(III) ion is six-coordinated by four secondary amines of the macrocycle, hydroxide anion and nitrophenolate anion.

Photophysical Properties of Highly Efficient Blue-Green Emitting Cationic Iridium (III) Complexes Containing Two 2-Phenylbenzothiazole Ligands and One Diphosphine Ligand

  • Yun, Seong-Jae;Song, Young-Kwang;Kim, Minji;Shin, Jaemin;Jin, Sung-Ho;Kang, Sung Kwon;Kim, Young-Inn
    • Bulletin of the Korean Chemical Society
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    • v.35 no.11
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    • pp.3199-3204
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    • 2014
  • Two novel phosphorescent heteroleptic cationic Ir(III) complexes, Ir(bt)2(dmpe) (Ir1) and Ir (bt)2(dppe) (Ir2), where bt is 2-phenylbenzothiazole, dmpe is 1,2-bis(dimethylphosphino)ethane, and dppe is 1,2-bis(diphenyl-phosphino) ethane, were designed and synthesized. Their photophysical and electrochemical properties and the X-ray structure of the Ir1 complex were investigated. The prepared Ir(III) complexes exhibited blue-green emissions at 503-538 nm with vibronic fine structures in dichloromethane solution and PMMA film, implying that the lowest excited states are dominated by ligand-based $^3{\pi}-{\pi}^*$ transitions. The ${\pi}$-acceptor ability of the diphosphine ancillary ligand leads to blue-shift emission. The room temperature photoluminescent quantum yields (PLQYs) of Ir1 and Ir2 were 52% and 45%, respectively, in dichloromethane solution. These high PLQYs resulted from steric hindrances by the bulky cationic iridium complexes. The crystal structure of Ir1 was determined by X-ray crystallography, which revealed that central iridium adopted a distorted octahedral structure coordinated with two bt ligands (N^C) and one dmpe ligand (P^P) showing cis C-C and trans N-N dispositions. The bent nature of the dmpe ligand resulted in a relatively wide bite angle of $83.83^{\circ}$ of P-Ir-P.

Novel Cationic 2-Phenylpyridine-based Iridium(III) Complexes Bearing an Ancillary Phosphine Ligand: Synthesis, Photophysics and Crystal Structure

  • Ma, Ai-Feng;Seo, Hoe-Joo;Jin, Sung-Ho;Yoon, Ung-Chan;Hyun, Myeong-Ho;Kang, Sung-Kwon;Kim, Young-Inn
    • 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.

Structure of a Copper(Ⅱ) Hexaazamacrotricyclic Complex : (1,3,6,9,11,14-Hexaazatricyclo[12.2.1.16,9]octadecane)-copper(Ⅱ) Perchlorate

  • Cheon Manseog;Suh Paik Myunghyun;Shin Whanchul
    • Bulletin of the Korean Chemical Society
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    • v.13 no.4
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    • pp.363-367
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    • 1992
  • The crystal structure of (1,3,6,9,11,14-hexaazatricycol[12.2.1.$1^{6,9}$]octadecane)copper(Ⅱ) perchlorate, Cu($C_{12}H_{26}N_6$)$(ClO_4)_2$, has been determined by the X-ray diffraction methods. The crystal data are as follows: Mr=516.9, triclinic, ${\alpha}=8.572\;(2)$, b=8.499 (3), c=15.204 (3) ${\AA}$, ${\alpha}=80.42\;(5),\;{\beta}=73.57\;(3),\;{\gamma}=69.82\;(4)^{\circ},\;V=994.2\;{\AA}^3,\;D_C=1.726\;gcm^{-3}$, space group $P{\tilde{1}},\;Z=2,\;{\mu}=21.27\;cm^{-1}&, F(000)=534 and T=297 K. The structure was solved by direct methods and refined by full-matrix least-squares methods to and R value of 0.081 for 1608 observed reflections measured with graphite-mono-chromated Mo Ka radiation on a diffractometer. There are two independent complexes in the unit cell. The two copper ions lie at the special positions (1/2, 0, 0) and (0, 1/2, 1/2)and each complex possesses crystallographic center of symmetry. Each Cu ion is coordinated to four nitrogen donors if the hexaazamacrotricyclic ligand and weakly interacts with two oxygen atoms of the perchlorate ions to form a tetragonally distorted octahedral coordination geometry. The Cu_N (sec), Cu_N(tert) and Cu_O coordination distances are 1.985 (14), 2.055 (14) and 2.757 (13) ${\AA}$ for the complex A and 1.996 (10), 2.040 (11) and 2.660 (13) ${\AA}$ for the complex B, respectively. The macrocycles in the two independent cations assume a similar conformation with the average r.m.s. deviation of 0.073 ${\AA}$. Two 1,3-diazacyclopentane ring moieties of the hexaazamacrotricyclic ligand are placed oppositely and almost perpendicularly to the square coordination plane of the ruffled 14-membered macrocycle. The secondary N atoms are hydrogen-bonded to the perchlorate O atoms with distances of 3.017 (23) and 3.025 (19) ${\AA}$ for the complexes A and B, respectively.

The Jahn-Teller Effect in the Iron Copper Spinel $CuFe_{2}O_{4}$ (철, 구리 스피넬 $CuFe_{2}O_{4}$의 Jahn-Teller 효과에 관한 연구)

  • 서정철;이민용
    • Journal of the Korean Magnetics Society
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    • v.5 no.2
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    • pp.123-127
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    • 1995
  • $CuFe_{2}O_{4}$ was accomplished by chemical rrethod and the crystallographic and magnetic properties have been studied by $M\"{o}ssbauer$ spectroscopy and X-ray diffraction. The slowly cooled sample is found to have a tetragonal spinel structure with the lattice constant $a=8.26{\pm}0.05{\AA},\;c=8.75{{\pm}}0.05{\AA}$. The $M\"{o}ssbauer$ spectra between the room temperature to the Curie temperature show that the $Cu_{2+}$ ions at octahedral site have the Jahn-Teller effect and the sample exhibits a structural phase transition near 630K due to the Jahn-Teller effect. The Curie temperature is found to be 690K and it is lower than that of ceramic method.

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Structural and Magnetic Properties of the Substituted YIG System (치환된 YIG계의 구조적 및 자기적 특성)

  • Choi, Seung-Han;Lee, Young-Bae
    • Korean Journal of Materials Research
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    • v.13 no.1
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    • pp.48-52
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    • 2003
  • The substituted yttrium iron garnet systems $Y_{ 3-x}$/Gd$_{x}$X$0.2_{0.2}$ $Fe_{4.8}$ $O _{12}$ (x = 0.2, 0.4, 0.6) have been investigated by means of X-ray diffraction, Mossbauer spectroscopy and SQUID. The X-ray diffraction patterns at room temperature confirm the samples to have a single phase of the garnet structure over the whole composition range. The lattice constants of all the samples linearly change with increasing x due to the size of substituted ions in the dodecahedral sites. $Y_{3-x}$ $Gd_{x}$ X$Fe_{4.8}$ $In_{0.2}$ $O_{12}$ system which $Y_{3-x}$ ions are substituted with Gd$^{ 3+}$ ions, the Mossbauer spectrum consists of three Zeeman sextets at room temperature, one due to the $Fe^{3+}$ ions on the octahedral(a-) sites and the others due to the $Fe^{3+}$ ions on the tetrahedral(d-, d'-) sites, respectively. From the hysteresis loop measured by means of SQUID over the whole composition range, the saturation magnetization $M_{s}$ and magnetic moments $\mu_{ B}$ per unit cell have been obtained. The increment of Gd-ion content causes $M_{s}$ and $\mu_{B}$ decrease while the increment of In-ion content does not.

Electronic state of LiNiO_2$ cathode materials for Li ion barriers (리튬 이차 전지로의 응용을 위한 LiNiO_2$ 양극 물질의 전자상태 연구)

  • 전영아;김양수;노광수
    • Proceedings of the Materials Research Society of Korea Conference
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    • 2003.11a
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    • pp.216-216
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    • 2003
  • The layered nickel oxides (LiNiO$_2$) have been studied for possible use as cathode materials i3l 4V lithium batteries. Although LiCoO$_2$ has been known as the best candidate material for Li-ion batteries, which produces the best performance LiNiO$_2$ is generally accepted as an attractive cathode material, because of its various advantages such as lower cost higher discharge capacity and better reversibility. In this investigation, we calculated the electric state of LiNiO$_2$ using DV-X$\alpha$ molecular orbital method in order to obtain the information of chemical bonding among the Li, Ni and O. In LiNiO$_2$, alternate layers of Li and Ni occupy the octahedral sites of a cubic close packing of oxide ions, making up a rhombohedral structure with an R-3m space group, Li in 3a, Ni in 3b, and O in 6c sites. On the basis of this, we made the cluster model and studied ionization of each atoms and interaction between atoms according to Mullilcen population analysis.

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High-Speed Deposition of Diamond Films by DC Plasma Jet (직류 플라즈마 제트를 이용한 고속 다이아몬드 막 증착기술)

  • Kim, Won-Kyu;Whang, Ki-Woong
    • Proceedings of the KIEE Conference
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    • 1992.07b
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    • pp.949-951
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    • 1992
  • A low pressure DC plasma jet has been used to obtain diamond films from a mixture of $CH_4$ and $H_2$ with high deposition rate (>1$\mu\textrm{m}$/min). The effects of the deposition conditions such as torch geometry, substrate temperature, gas mixing ratio, chamber pressure, axial magnetic field on the diamond film properties such as morphology, purity, uniformity of the film and deposition rate, etc. have been examined with the aid of Scanning Electron Microscopy, X-Ray Diffraction, and Raman Spectroscopy. Both the growth rate and particle size increased rapidly for low methane concentrations but saturated and the morphology changed from octahedral to cubic structure when the concentration exceeded 1.0 %. Higher growth rates (>1.5${\mu}m$/min) can be obtained by applying an axial magnetic field to the DC plasma jet. Diamond obtained from the magnetized plasma jet also shows a sharp peak at 1332.5$cm^{-1}$ in the Raman Spectra and this result implies that higher growth rate with a good quality diamond films can he obtained by applying an external magnetic field to the plasma jet.

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Use of Hydrazine for Pitting Corrosion Inhibition of Copper Sprinkler Tubes: Reaction of Hydrazine with Corrosion By-Products

  • Suh, Sang Hee;Kim, Sohee;Suh, Youngjoon
    • Corrosion Science and Technology
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    • v.16 no.5
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    • pp.247-256
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    • 2017
  • The feasibility of using hydrazine for inhibiting pitting corrosion in copper sprinkler tubes was investigated by examining microscopical and structural evolution of corrosion by-products with SEM, EDS, and XRD. Hydrazine removed dissolved oxygen and reduced CuO and $Cu_2O$ as well. The stable phase was changed from CuO to $Cu_2O$ or Cu depending on hydrazine concentration. Hydrazine concentration of 500 ppm could convert all CuO corrosion by-products to $Cu_2O$. In a tightly sealed acryl tube filled with aqueous solution of 500 ppm hydrazine, octahedral $Cu_2O$ particles were formed while plate-like structures with high concentration of Cu, O, N and C were formed near a corrosion pit. The inside structure of a corrosion pit was not altered by hydrazine aqueous solution. Uniform corrosion of copper was almost completely stopped in aqueous solution of 500 ppm hydrazine. Corrosion potential of a copper plate was linearly dependent on log (hydrazine concentration). The concept of stopping pitting corrosion reaction by suppressing oxygen reduction reaction could be verified by applying this method to a reasonable number of real sprinkler systems before full-scale application.