• 제목/요약/키워드: Octahedral structure

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Local Structure Refinement of the $BaFe_{1-x}Sn_xO_{3-y}$ System with Fe K-Edge X-Ray Absorption (XANES/EXAFS) Spectroscopy

  • 김민규;곽기섭;로권선;여철현
    • Bulletin of the Korean Chemical Society
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    • 제18권7호
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    • pp.743-749
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    • 1997
  • Local structure refinement of the BaFe1-xSnxO3-y system (x=0.00-0.50) has been carried out with Fe K-edge x-ray absorpion spectroscopic studies. It is found out that the Fe ions are placed in two different symmetric sites such as tetrahedral and octahedral sites in the compounds by comparison with Fe K-edge x-ray absorption near edge structure (XANES) spectrum of the γ-Fe2O3 compound as a reference. Small absorption peaks of dipole-forbiden transitions appear at a pre-edge region of 7111 eV due to the existence of Fe ions in the tetrahedral and octahedral sites. The peak intensity decreases with the substitution amount of Sn ion. Three different absorption peaks of 1s→4p dipole-allowed transition appear on the energy region between 7123 and 7131 eV. The peaks correspond to 1s→4p main transition of Fe ions in tetrahedral and octahedral sites and 1s→4p transition followed by the shakedown process of ligand to metal charge transfer. The bond distances between Fe ions in the tetrahedral site and nearest neighboring oxygen atom (Fe-4O), and those in octahedral site (Fe-6O) are determined with the extended x-ray absorption fine structure (EXAFS) analysis. Two different interatomic distances increase with the substitution amount of Sn ion and also the bond lengths of Fe-4O are shorter than those of Fe-6O in all compounds.

Synthesis, Structure, and Peroxidase Activity of an Octahedral Ru(III) Complex with a Tripodal Tetraamine Ligand

  • Cho, Jang-Hoon;Kim, Kwan-Mook;Noh, Dong-Youn;Lee, Hong-In
    • Bulletin of the Korean Chemical Society
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    • 제32권11호
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    • pp.3904-3908
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    • 2011
  • A new octahedral Ru(III) complex with a tripodal tetraamine ligand, tpea = tris[2-(1-pyrazoyl)ethyl]amine, has been prepared and characterized. The single crystal X-ray crystallographic study of the complex revealed that the complex has a near octahedral geometry with the tetradentate ligand and two chloride ions. Peroxidase activity was examined by observing the oxidation of 2,2'-azinobis(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS) with hydrogen peroxide in the presence of the complex. Amount of $ABTS^{+{\bullet}}$ generated during the reaction was monitored by UV/VIS and EPR spectroscopies. After the initiation of the peroxidase reaction, $ABTS^{+{\bullet}}$ concentration increases and then decreases after certain time, indicating that both ABTS and $ABTS^{+{\bullet}}$ are the substrates of the peroxidase activity of the Ru(III) complex.

Electrochemical Synthesis of Octahedral Nanostructured PbF2

  • Lee, Joon-Ho;Choi, Jin-Sub
    • Bulletin of the Korean Chemical Society
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    • 제32권2호
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    • pp.463-466
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    • 2011
  • In this work, we investigate anodization of Pb in ethylene glycol containing small amount of $NH_4F$, demonstrating that ${\beta}-PbF_2$ particles with octahedral morphology can be prepared by adjusting the applied potential and anodizing time. FE-SEM images and XRD measurements of anodic nanostructures as a function of anodizing time clearly show that PbO is first formed on Pb. Subsequently, a local dissolution of PbO leads to formation of skeleton structure of PbO, releasing $Pb^{2+}$ ions in the electrolyte. The lead ions can be precipitated on the walls or intersection of the skeleton walls when the concentration of lead ions is saturated. The method described in this article shows the feasibility of formation of metal fluoride crystal by anodization of metal in a fluoride containing solution.

산처리 과정에 따른 벤토나이트의 결정구조 변화 (The Effects of Acid Treatment of Bentonite on Its Crystal Structure)

  • 윤소정;문희수
    • 자원환경지질
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    • 제27권6호
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    • pp.507-521
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    • 1994
  • Bentonite occurs in the Janggi Conglomerate of Tertiary age and consists mainly of montmorillonite with Mg as predominant interlayer cations. The bentonite was reacted with various concentrations of sulfuric acid (0.8~1.5M) for various reaction time (1-10h) at $103^{\circ}C$. Cation exchange capacity, exchangeable cations, surface area and solid acidity of the original bulk and acid activated bentonites were measured. Chemical analysis, X-ray diffraction, differential thermal analysis and infrared spectroscopy were used to characterize the changes in structure and properties of the acid activated bentonite. The dissolution of octahedral cations occurs not only from the edge of the clay platelets but also throughout the whole clay structure creating vacant octahedral sites. These lattice defects are created by $H^+$ diffused into the smectite layers. The cations leached possibly from the octahedral sheets are adsorbed on the interlayer exchange sites. They are exchanged with hydronium ions again by stronger acid attack. These reactions create wedge-shaped pores resulting in the increase of the surface area and the changes the morphology in the lattice structure.

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Synthesis and Characterization of Mononuclear Octahedral Fe(III) Complex Containing a Biomimetic Tripodal Ligand, N-(Benzimidazol-2-ylmethyl)iminodiacetic Acid

  • Moon, Do-Hyun;Kim, Jung-hyun;Lah, Myoung-Soo
    • Bulletin of the Korean Chemical Society
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    • 제27권10호
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    • pp.1597-1600
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    • 2006
  • The mononuclear iron complex 1, $Fe^{III}$(Hbida)Cl($H_2O$), was synthesized using a tripodal tetradentate ligand, N-(benzimidazol-2-ylmethyl)iminodiacetic acid (H3bida), which has two carboxylate groups, one benzimida- zoyl group, and one tertiary amine where it serves as a tetradentate chelating ligand for the octahedral Fe(III) ion. The four equatorial positions of the octahedral complex are occupied by two monodentate carboxylates, a benzimidazole nitrogen, and an oxygen of a water molecule. One of the axial positions is occupied by an apical nitrogen of the Hbida and the other by a chloride anion. The mononuclear octahedral complex 1 mimics the geometry of the key intermediate structure of the catalytic reaction cycle proposed for the FeSODs, which is a distorted octahedral geometry with three histidyl imidazoles, an aspartyl carboxylate, a superoxide anion, and a water molecule. The redox potential of complex 1, $E_{1/2}$ is -0.11V vs. Ag/AgCl (0.12 V vs. NHE), which is slightly lower than those reported for the most FeSODs. The magnetic susceptibility of complex 1 at room temperature is 5.83 $\mu$B which is close to that of the spin only value, 5.92 $\mu$B of high-spin d5 Fe(III).

The Effect of Solvent on the Dipole Moments for Organotin(Ⅳ) Complexes

  • Ahn, Sang-Woon;Kim, Dong-Heu;Oh, Se-Woung
    • Bulletin of the Korean Chemical Society
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    • 제5권1호
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    • pp.3-16
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    • 1984
  • The effect of solvent on the dipole moments for (chloromethyl) stannanes has been investigated by applying EHT calculation for the isomers of trigonal bipyramidal Sn(Ⅳ)$Cl_4X$ and $Cl_n$Sn(Ⅳ) $(CH_2Cl)_{4-n}$, octahedral Sn(Ⅳ)$Cl_42X$ and $Cl_nSn$(Ⅳ)$(CH_2Cl)_{4-n}$ 2X type complexes in dioxane and ethylacetate solutions (X: dioxane or ethylacetate). For Sn(Ⅳ)$Cl_4$ in dioxane solution, the calculated dipole moment for the trigonal bipyramidal Sn(Ⅳ)$Cl_4X$ type complex [isomer (b)] is closer to the experimental dipole moment than octahedral Sn(Ⅳ)$Cl_4X$2X type complexes. This calculated dipole moment suggests that Sn(Ⅳ)$Cl_4X$ may have the trigonal bipyramidal structure in dioxane solution. However, the calculated dipole moment for octahedral $Cl_3$Sn(Ⅳ) ($CH_2$Cl)2X type complex [Isomer (d)], ClSn(Ⅳ)(CH2Cl)32X type complex [Isomer(k)] and Cl2Sn(Ⅳ)(CH2Cl)22X type complex [Isomer(h)] are closer to the experimental dipole moments than other isomers for octahedral complexes and trigonal bipyramidal complexes. Such theoretical results indicate that $Cl_3Sn$(Ⅳ )($CH_2Cl$), ClSn(Ⅳ)$(CH_2Cl)_3$ and $Cl2Sn$(Ⅳ)$(CH_2Cl)_2$ complexes may have octahedral structures, Isomer(d), (k) and (h) in ethylacetate solution, respectively.

Irradiation Induced Modifications of Amorphous Phase in GeTe Film

  • Park, Seung Jong;Jang, Moon Hyung;Ahn, Min;Yang, Won Jun;Han, Jeong Hwa;Cho, Mann-Ho
    • Applied Science and Convergence Technology
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    • 제24권3호
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    • pp.60-66
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    • 2015
  • The modified amorphous GeTe formed by pulsed laser irradiation in as-grown GeTe has been analyzed in terms of variations of local bonding structure using extended x-ray absorption fine structure (EXAFS). The modified GeTe film has octahedral-like Ge-Te bonding structure that can be effectively induced by irradiation process. The EXAFS data clearly shows that the irradiation can lead to reduction of the average coordination number. Variations in the transition temperature for the irradiated film during crystallization can be described by the presence of octahedral-like local structure.

Synthesis and Characterization of Nickel(II) Tetraaza Macrocyclic Complex with 1,1-Cyclohexanediacetate Ligand

  • Lim, In-Taek;Kim, Chong-Hyeak;Choi, Ki-Young
    • 대한화학회지
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    • 제62권6호
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    • pp.427-432
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    • 2018
  • The reaction of [$[Ni(L)]Cl_2{\cdot}2H_2O$ (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[$14,4,0^{1.18},0^{7.12}$]docosane) with 1,1-cyclohexanediacetic acid ($H_2cda$) yields mononuclear nickel(II) complex, [$Ni(L)(Hcda^-)_2$] (1). This complex has been characterized by X-ray crystallography, electronic absorption, cyclic voltammetry and thermogravimetric analyzer. The crystal structure of 1 exhibits a distorted octahedral geometry with four nitrogen atoms of the macrocycle and two 1,1-cyclohexanediacetate ligands. It crystallizes in the triclinic system P-1 with a = 11.3918(7), b = 12.6196(8), $c=12.8700(8){\AA}$, $V=1579.9(2){\AA}^3$, Z = 2. Electronic spectrum of 1 also reveals a high-spin octahedral environment. Cyclic voltammetry of 1 undergoes one wave of a one-electron transfer corresponding to $Ni^{II}/Ni^{III}$ process. TGA curve for 1 shows three-step weight loss. The electronic spectra, electrochemical and TGA behavior of the complex are significantly affected by the nature of the axial $Hcda^-$ ligand.

Ligand Field Approach to $4d^{1}$ Magnetism Based on Intermediate Field Coupling Scheme

  • 최진호;김종영
    • Bulletin of the Korean Chemical Society
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    • 제18권9호
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    • pp.976-981
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    • 1997
  • The magnetic susceptibilities of molybdenum ions with 4d1 electronic configuration in the octahedral crystal field were calculated on the basis of ligand field theory. The experimental magnetic susceptibilities for molybdenum ions, which are stabilized at the octahedral site in the perovskite lattice of Ba2ScMoⅤO6 and Sr2YMoⅤO6, were compared with the theoretical ones. We have tried to fit their temperature dependence of magnetic susceptibility with ligand field parameters, spin-orbit coupling constant ζSO, and orbital reduction parameter κ according to intermediate field coupling and strong field theory. Strong field coupling theory could not explain experimental curves without unrealistically large axial ligand field, since it ignores the mixing up between different state via spin-orbit interaction and ligand field. On the other hand, the intermediate field coupling theory could successfully reproduce experimental data in octahedral and trigonal ligand field. The fitting result demonstrates not only the fact that spin-orbit interaction is primarily responsible for the variation of magnetic behavior but also the fact that effective orbital overlap, enhanced by cubic crystal structure, reduces significantly orbital angular momentum as indicated by κ parameter.

가변형상 트러스구조물의 자세제어 (Configuration Control of Vaiable-Geometry Truss Structures)

  • 노태환;김태익;박현철;권영두
    • 대한기계학회논문집A
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    • 제20권9호
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    • pp.2854-2865
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    • 1996
  • The concept of variable-geometry truss structure(VGTS) is introduced as a class of actively controlled adaptive structure. VGTS can purposefully vary its geometric configurations by changing the lengths of some members of the structure. General kinematics and inverse kinematics of a statically determinate VGTS(variable geometry truss structure) are studied. The solution technique is based on the Jacobian matrix obtained via joint equilibrium equations. Pseudoinverse control method is applied to resolve the redundancy of a large VGTS. two types of actuator layout of octahedral type VGTS, VG truss and Stewart platform, are compared. Introducing the concept of performance index, Stewart platform based layout was found to has less consumption energy and manipulation time. A functional VGTS model with 3 octahedral modules is designed and manufactured for the labaratory demonstration. Six vertically located length-variable members are used to create general 6 d.o.f. motions.