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101.
R. B. King 《Russian Chemical Bulletin》1993,42(8):1283-1291
Methods derived from topology and graph theory indicate that the deltahedral boranes B
n
H
n
2– and the corresponding carboranes C2Bn–2H
n
(6 n 12) may be regarded as three-dimensional delocalized aromatic systems in which surface bonding and core bonding correspond to -bonding and -bonding, respectively, in planar polygonal two-dimensional hydrocarbons CinnH
n
(n–6)+ (n=5/7). The two extreme types of topologies which may be used to model core bonding in deltahedral boranes and carboranes are the deltahedral (D
n
) topology based on the skeleton of the underlying deltahedron and the complete (K
n
) topology based on the corresponding complete graph. Analyses of the Hoffmann-Lipscomb LCAO extended Hückel computations, the Armstrong—Perkins—Stewart self-consistent molecular orbital computations, and SCF MOab initio GAUSSIAN-82 computations on B6H6
2– indicate that the approximation of the atomic orbitals by the sum of the molecular orbitals, as is typical in modernab initio computations, leads to significantly weaker apparent core bonding approximated more closely by deltahedral (D
n
) topology than by complete (K
n
) topology.This work was presented at the Workshop The Modern Problems of Heteroorganic Chemistry sponsored by the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (May 8–13, 1993).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1353–1360, August, 1993. 相似文献
102.
Tian-Ling Ren Lin-Tao Zhang Li-Tian Liu Zhi-Jian Li 《Journal of Sol-Gel Science and Technology》2002,24(3):271-274
A novel silicon-based PbTiO3/Pb(Zr,Ti)O3/PbTiO3 (PT/PZT/PT) sandwich structure has been prepared using a sol-gel method. The annealing temperature is greatly reduced compared with those structures without PT layers. Capacitance-voltage (C-V), leakage current-voltage (I-V), polarization-field (P-E), dielectric-frequency response and polarization fatigue of the sandwich structure are examined. The relative dielectric constant, the coercive field and the remanent polarization of the PZT films are measured to be about 900, 18 kV/cm and 16 C/cm2 respectively. The current density is less than 5 × 10–9 A/cm2 below 200 kV/cm. The dielectric constant of the structure remains constant at low frequency, and decreases to some degree at high frequency. The retained polarization does not change significantly after 8 × 109 read/write cycles. The PZT films are proved to have very good dielectric and ferroelectric properties. The new PT/PZT/PT sandwich structure can be valuable for memory devices and other applications. 相似文献
103.
E. V. Alekseev E. V. Suleimanov E. V. Chuprunov G. K. Fukin L. G. Alekseeva 《Journal of Structural Chemistry》2005,46(5):936-940
The crystal structure of KAsUO6·3H2O was solved at 100 K and 293 K. KAsUO6·3H2O at T = 100 K: tetragonal, P4/ncc, a = 7.2037(6) Å, c = 17.811(2) Å; Z = 4, R1 = 0.0263, wR2 = 0.0546, for 618 independent reflections; at T = 293 K: tetragonal, P4/ncc, a = 7.1600(4) Å, c = 17.746(1) Å; Z = 4, R1 = 0.0263, wR2 = 0.0433 for 427 independent reflections. The results of X-ray analysis are compared with our previous data on heat capacity of this compound, and changes that take place in the structure at elevated temperature are considered. 相似文献
104.
Hyungrak Kim 《Journal of solid state chemistry》2005,178(6):1935-1939
The compound Ca14MnP11 crystallizes in the Ca14AlSb11 structure type with the tetragonal space group I41/acd (Z=8) and lattice parameters of , c=20.7565(9) at 90 K. The structure consists of MnP49− tetrahedron, P37− trimer, 4 P3− isolated anions and 14 Ca2+ cations. Similar to other compounds of this structure type containing phosphorous, the P37− trimer has a central P atom that is best modeled in the structure as being equally split between two sites. In addition, there is no additional distortion of the manganese-containing tetrahedron compared with the main group analog, Ca14GaP11, suggesting that the Mn oxidation state is Mn2+. Temperature-dependent magnetic susceptibility shows that the compound is paramagnetic over the entire temperature range measured (2-300 K). The data can be fit with a modified Curie-Weiss law and provide an effective magnetic moment of 5.80 (2) B.M. with a Weiss constant of −2.13(2) K and . This moment is significantly higher than those measured for any of the Mn-containing analogs and is consistent with Mn2+. This result will be discussed in light of the electron counting scheme for Mn compounds of the Ca14AlSb11 structure-type. 相似文献
105.
O. G. Shakirova D. Yu. Naumov Yu. G. Shvedenkov N. I. Alferova G. V. Dolgushin L. G. Lavrenova 《Journal of Structural Chemistry》2003,44(4):642-649
A new trinuclear nickel(II) complex with 4-(pyridyl-2)-1,2,4-triazole (pytrz), [Ni3(pytrz)6(H2O)6](NO3)6, has been synthesized, and its crystal structure has been determined. The compound was studied by X-ray phase analysis (XRPA), magnetochemical measurements, and electronic and IR spectroscopy. 相似文献
106.
Tapan Kumar Lal John F. Richardson Mark S. Mashuta Robert M. Buchanan Rabindranath Mukherjee 《Polyhedron》1997,16(24):1248-4336
Synthesis and characterization of a nitrite-bound copper(II) compound [CuL4)2(ONO)]ClO4 have been achieved (L4 = 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine]. The bidentate ligand L4 provides a pyridine and a pyrazole donor site; however, they are separated by a methylene spacer. The complex has been structurally characterized and it belongs to only a handful of complexes having nitrito-bound mononuclear copper(II) centre. The metal atom has a distorted square pyramidal geometry with the copper atom displaced from the equatorial plane by 0.25 Å. In MeCN solution the green complex exhibits a broad ligand-field transition at 655 nm with a shoulder at 675 nm and in dichloromethane-toluene glass (80 K) it exhibits an EPR spectral feature characteristic of the unpaired electron in the dx2−y2 orbital. Variable-temperature (80–300 K) magnetic susceptibility measurements in the solid state as well as room temperature measurement in MeCN solution reveal mononuclear magnetically dilute copper(II) centre. When examined by cyclic voltammetry (MeCN solution) it displays electrochemically irreversible CuII---CuI response [cathodic peak potential, Epc (V vs saturated calomel electrode (SCE)): −0.32]. An oxidative response is observed at 1.14 V, probably due to bound-nitrite oxidation and is partially removed to generate a solvated complex at the electrode surface. The latter species gives rise to reversible CuII---CuI redox response [
]. 相似文献
107.
L. F. Chertanova B. I. Buzykin A. A. Gazikasheva M. P. Sokolov 《Russian Chemical Bulletin》1992,41(12):2162-2167
The crystal and molecular structures of the products of the halogenation of the dimorpholide of ethoxyvinylphosphonic acid were determined by the method of x-ray structure analysis. It was established that (dimorpholinophosphoryl)chloroacetaldehyde only exists in the crystals as the Z-enol [(Z)-1-hydroxy-2-(dimorpholinophosphoryl)-2-chloroethene] with intra- and intermolecular H-bonds (=CH...O=P and OH...O=P). The (dimorpholinophosphoryl)dibromomethane forms centrosymmetric eight-membered cyclic dimers in the crystals due to intermolecular CH...O=P H-bonds. The structure of the morpholine and phosphoryl groups in both compounds was discussed.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center, Russian Academy of Sciences, 420083 Kazan'. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2730–2737, December, 1992. 相似文献
108.
The first isocyanide ligated hexanuclear zirconium halide cluster is reported. The unoxidized [(Zr6Be)Cl12(CNXyl)6] (CNXyl = 2,6-dimethylphenyl isocyanide) was obtained from the solid state precursor K3Zr6Cl15Be by dissolution in CH3CN in the presence of CNXyl. The CNXyl ligands occupy all the axial positions on the cluster. The compound was recrystallized from CH2Cl2 and Et2O. [(Zr6Be)Cl12(CNXyl)6].2CH2Cl2 crystallizes in the space group
(#2) with a = 12.092(5) Å, b=12.728(5) Å, c = 14.102(8) Å, = 104.98(4)°, =107.11°, = 100.94°, V = 1919(2) Å3, Z = l, R = 11.3% and R
W
= 27.0%. For the bound isocyanide ligands, v
CN increases to 2140 cm–1. 相似文献
109.
The molecular structures of (benzoyl)benzo-12-crown-4 (a=22.387,b=4.503,c=16.167 Å,d
calc=1.34 g cm–3,Z=4, space groupP21
nc, DAR-UM, Cu-K,R=0.056) and (diphenylacetyl)benzo-12-crown-4 (a=8.866,b=23.337,c=10.737 Å;d
calc=1.25 g cm–3,Z=4, space groupP212121, DAR-UM, Cu-K, R=0.056) have been investigated. The differences in the conformations of the macrocycles and the degree of conjugation between the benzene ring orbitals and the lone pairs on the adjacent oxygen atoms in the macrocycle are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1906–1911, November, 1993. 相似文献
110.
Crystals of 4(C2H5)4N+F– · 11H2O are orthorhombic, space groupPna21, witha=16.130(3),b=16.949(7),c=17.493(7) Å, andZ=4. The structure was shown to be a clathrate hydrate containing infinite chains of edge-sharing (H2O)4F– tetrahedra extending parallel to thea axis. The chains are laterally linked by bridging water molecules to form a three-dimensional hydrogen-bonded anion/water framework. The ordered (C2H5)4N+ cations occupy the voids in two open channel systems running in theb andc directions. FinalR
F
=0.091 for 2278 observed MoK data measured at 22°C.
Supplementary Data: relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82010 (20 pages).Dedicated to Professor H. M. Powell. 相似文献