Characteristic features of the magnetic ordering of Dy3+ ions in a monoclinic RbDy(WO4)2 single crystal

The investigation of the specific heat of a RbDy(WO₄)₂ single crystal at temperatures 0.2–2.5 K and in magnetic fields up to 2 T are reported. The temperature dependence of the specific heat near T _N=0.818 K is compared with the predictions for different models. The 2D Ising model describes satisfactorily C(T) below T _N, while for T>T _N none of the theoretical models agree with the behavior of C(T) of RbDy(WO₄)₂. The H-T phase diagram for H∥c is complicated and possesses a triple point, where regions of existence of three magnetic phases converge. The magnetic ordering is analyzed from the standpoint of the Jahn-Teller nature of the structural phase transitions occurring in RbDy(WO₄)₂ at higher temperatures. It is shown that the form of the phase diagram depends on the direction of the vector H, for the general case of an arbitrary direction of H, two phase transitions can occur with increasing field. Fiz. Tverd. Tela (St. Petersburg) 41, 491–496 (March 1999)     

LARGE-SCALE PATHOLOGY OF UNIVERSES WITH VII0×VIII ISOMETRIES

The goal of this paper is to show somewhat unexpected globally pathologic properties in universes described by a class of static planary symmetric exact solutions with G ₆-group of motion. In order to achieve this aim, the Killing vectors, the null geodesics and the Penrose diagrams corresponding to different expressions of g ₄₄=–e ^2f(z), with f(z) solutions of Einstein's equations, have been employed. Finally, woking in a particular gauge, we focus on the behaviour of the radiating electromagnetic modes and derive the observable components of E and B and the expressions of the essential component of the Umov-Poynting vector.     

The structural transformation of monoclinic [(R)-C5H14N2][Cu(SO4)2(H2O)4]·2H2O into orthorhombic [(R)-C5H14N2]2[Cu(H2O)6](SO4)3: crystal structures and thermal behavior

Single crystals of [(R)-C₅H₁₄N₂][Cu(SO₄)₂(H₂O)₄]·2H₂O (1) were grown through the slow evaporation of a solution containing H₂SO₄, (R)-C₅H₁₂N₂ and CuSO₄·5H₂O. These crystals spontaneously transform to [(R)-C₅H₁₄N₂]₂[Cu(H₂O)₆](SO₄)₃ (2) over the course of four days at room temperature. The same single crystal on the same mounting was used for the determination of the structure of (1) and the unit cell determination of (2). A second single crystal of the transformed batch has served for the structural determination of (2). Compound 1 crystallizes in the noncentrosymmetric space group P2₁ (No. 4) and consists of trimeric [Cu(SO₄)₂(H₂O)₄]^2? anions, [(R)-C₅H₁₄N₂]²⁺ cations and occluded water molecules. Compound 2 crystallizes in P2₁2₁2 (No. 18) and contains [Cu(H₂O)₆]²⁺ cations, [SO₄]^2? anions and occluded water molecules. The thermal decompositions of compounds 1 and 2 were studied by thermogravimetric analyses and temperature-dependent X-ray diffraction.     

Quantum deformation of lorentz group

A one parameter quantum deformationS _μ L(2,ℂ) ofSL(2,ℂ) is introduced and investigated. An analog of the Iwasawa decomposition is proved. The compact part of this decomposition coincides withS _μ U(2), whereas the solvable part is identified as a Pontryagin dual ofS _μ U(2). It shows thatS _μ L(2,ℂ) is the result of the dual version of Drinfeld's double group construction applied toS _μ U(2). The same construction applied to any compact quantum groupG _c is discussed in detail. In particular the explicit formulae for the Haar measures on the Pontryagin dualG _d ofG _c and on the double groupG are given. We show that there exists remarkable 1-1 correspondence between representations ofG and bicovariant bimodules (“tensor bundles”) overG _c . The theory of smooth representations ofS _μ L(2,ℂ) is the same as that ofSL(2,ℂ) (Clebsh-Gordon coefficients are however modified). The corresponding “tame” bicovariant bimodules onS _μ U(2) are classified. An application to 4D ₊ differential calculus is presented. The nonsmooth case is also discussed.     

Theoretical study on the influence of different NˆN ligands on the electronic structures and optoelectronic properties of heteroleptic Iridium(III) complexes

DFT/TDDFT calculations were carried out to investigate the electronic structures, absorption and phosphorescence properties of a series of heteroleptic Ir(III) complexes consisting of two N-heterocyclic carbene ligands and a conjugated bicyclic N,N′-heteroaromatic (N?N) ligand. On the basis of the results reported herein, we attempt to explain the experimental observations according to which complex (mpmi)₂Ir(pybi) (1) [Hmpmi = 1-(4-tolyl)-3-methyl-imidazole; Hpybi = 2-(pyridin-2-yl)-1H-benzo[d]imidazole] emits green light with an extremely high-quantum phosphorescence efficiency (Φ _PL ) of 79.3%, while a relatively lower Φ _PL (only 11%) was measured for (fpmi)₂Ir(tfpypz) (2) [fpmi = 1-(4-fluorophenyl)-3-methylimdazolin-2-ylidene-C, C^2′; tfpypz = 2-(3-(trifluoromethyl)-1H-pyrazol-5-yl)pyridinato] emitting blue light by tuning the N?N ligands. Besides, we also designed (fpmi)₂Ir(pyN3) (3) [pyN3H = 2-(5-(trifluoromethyl)-2H-1,2,4-triazol-3-yl)pyridine] and (fpmi)₂Ir(pyN4) (4) [pyN4H = 2-(1H-tetrazol-5-yl)pyridine] to explore the influence of electron-withdrawing substituents on N?N ligands on the electronic and optical properties of these Ir(III) complexes. The results revealed that electron-withdrawing substituents can stabilise both HOMOs and LUMOs and induce HOMO–LUMO energy gap change. Moreover, the emission properties can be significantly tuned by introducing different N?N ligands. While new insights were gained on structural and electronic properties, the extremely high Φ _PL of 1 was found to be not inherent to spin-orbital coupling effects, but determined by its large transition dipole moment (μ_{S 1}) upon S ₀–S ₁ transition compared with that of 2. On the basis of these results, the designed complexes 3 and 4 are considered to be the promising candidates for blue-emitting phosphorescence materials with higher Φ _PL than the complex 2.     

EPR Study of Single Crystals of PROXYLs

Electron paramagnetic resonance study of the single crystals of two PROXYLs, trans-2,5-bis(4-methylphenyl)-2,5-dimethylpyrrolidine-1-oxy [(±)-1] and trans-2-(4-methylphenyl)-2,5-dimethyl-5-phenylpyrrolidine-1-oxy [(±)-2] was conducted. The obtained spectra were always fitted well by a single Lorentzian. The principal g-values (g _x , g _y , g _z ) of (±)-1 and (±)-2 were determined as (2.00990, 2.00639, 2.00266) and (2.01106, 2.00742, 2.00389), respectively. The profiles of half width at half maximum (HWHM) depending on two polar angles, θ and ϕ, were measured in all directions. The angular profiles of the exchange interaction (|J ₀|) were attempted to be estimated by dividing the experimental HWHM by the calculated total second moment (M ₂ ^tot) with the crystallographic data. For (±)-1, |J ₀| along the c-axis was estimated to be much larger than that along the a- or b-axis. This suggests that (±)-1 is a one-dimensional magnet along the c-axis. Authors' address: Yohei Noda, Electron Spin Chemistry Laboratory, Department of Chemistry, Graduate School of Science, Kyoto University, 606-8502 Kyoto, Japan     

Measurement of beam quality factor (M) by slit-scanning method

Beam quality factor (M²) and far-field scattering angle of LD end-pump Nd : YVO₄ laser were measured by slit-scanning method. The experimental results showed that the laser operated on a multi-mode state. The corresponding analytical treatments for slit-scanning method and M² factor measurement also were presented in this paper.     

The Dynamics of Intramolecular Excited State Relaxation of <Emphasis Type="Italic">N</Emphasis>-Anthryl Substituted Pyridinium Cations

N-(1-Anthryl)-2,4,6-trimethyl-pyridinium (I), N-(2-anthryl)-2,4,6-trimethyl-pyridinium (II) and 10-(1-anthryl)-1,2,3,4,5,6,7,8-octahydro-acridinium cations (III) with anomalously high fluorescence Stokes shift have been investigated. Fluorescence kinetics analysis at various temperatures showed that in the range 293–77 K, the radiative deactivation rate constants (k_f) increase by 5.5 to 30 times. The low-temperature time-resolved emission spectra of I–III were found to be consistent with the model: A A^* B^* where A^* is the local excited twisted form and B^* is the relaxed more planar, bent conformer of the molecule. The rate constants of the excited relaxed state formation (k₁) and back reaction (k_–1) of compounds studied were estimated.     

Transmission Electron Microscopy Study of Polymorphism in Barium Gallate BaGa2O4

Polymorphism in barium gallate BaGa₂O₄ was studied using electron diffraction and high resolution electron microscopy. Three modifications of BaGa₂O₄ with structures closely related to the high-temperature α-form were observed. The phase transitions from γ-BaGa₂O₄ (a _γ = 18.6143(2) Å = 2<formula><radical><radicand>3</radicand></radical></formula>a _α, c _γ = 8.6544(1) Å = c _α, S.G. P6₃) to β-BaGa₂O₄ (a _β = 2a _α, c _β = c _α S.G. P6₃) and to the new δ-polymorph having a monoclinic structure (a _δ = c _α, b _δ = 2a _α + b _α, c _δ = 2b _α and β ≈ 92°, S.G. P2₁/c) were induced by electron beam irradiation. High resolution electron microscopy (HREM) observations allow to establish the close similarity between the structures of δ-BaGa₂O₄ and β-SrGa₂O₄. The γ→β and β→δ transitions involve a rearrangement of oxygen atoms in the BaO layers together with a tilting distortion of the tetrahedral framework. The microstructure of the δ-phase is characterised by the presence of numerous translation and orientation domains.     

Parallel and automated library synthesis of 2-long alkyl chain benzoazoles and azole[4,5-<Emphasis Type="BoldItalic">b</Emphasis>]pyridines under microwave irradiation

Summary A versatile route to 40-membered library of 2-long alkyl chain substituted benzoazoles (1 and 2) and azole[4,5-b]pyridines (3 and 4) via microwave-assisted combinatorial synthesis was developed. The reactions were carried out in both monomode and multimode microwave oven. With the latter, all reactions were performed in high-throughput experimental settings consisting of an 8×5 combinatorial library designed to synthesize 40 compounds. Each step, from the addition of reagents to the recovery of final products, was automated. The microwave-assisted N-long chain alkylation reactions of 2-alkyl-1H-benzimidazole (1) and 2-alkyl-1H-benzimidazole[4,5-b] pyridines (3) were also studied.     

The effect of ligands on the first hyperpolarizabilities of rich d electron molecular system: iridium clusters,a TDDFT study

A systematically varied series of tetrahedral iridium clusters have been studied using a TDDFT method focusing on their electronic and nonlinear optical properties. The clusters W₂Ir₂(CO)₁₀(η⁵-C₅H₄Me)₂ (1), WIr₃(μ-dppe)(CO)₉(η⁵-C₅H₄Me (2), W₂Ir₂(μ-L)(CO)₈(η⁵-C₅H₄Me)₂(L = dppe 3, dppf 4), Ir₄(μ-L)(CO)₁₀(L = dppm 5, dppe 6, Ph₂P(CH₂)₃PPh₂ 7, Ph₂P(CH₂)₄PPh₂ 8, (Ph₂P)₂CHMe 9), Ir₄(CO)₁₀(phen)(phen = 1,10-phenanthroline) (10) exhibit the first static hyperpolarizabilities of medium magnitude (β _tot ～ 10 × 10^?30esu). The origination of β is discussed in terms of the electronic structure calculation and the expanded orbital decomposition scheme. The result suggests the origination of β for all the clusters are mainly d–d electron transitions intra metal skeleton, and d–π* electron transitions from metals to carbonyls. For cluster 5, which contains the ferrocenyl group, the main origination of β involves charge transfer from d orbitals of ferrocene to d orbirals of Ir and W.     

Ionic liquid-promoted multi-component reaction: novel and efficient preparation of pyrazolo[3,4-<Emphasis Type="Italic">b</Emphasis>]pyridinone,pyrazolo[3,4-<Emphasis Type="Italic">b</Emphasis>]-quinolinone and their hybrids with pyrimidine nucleoside

The utilization of an ionic liquid, [bmim][BF₄] as both reaction medium and promoter for a multi-component reaction of aldehyde (1) and 5-amino-3-methyl-1-phenylpyrazole (2) with Meldrum acid (3) or dimedone (5) is studied. From this reaction, pyrazolo[3,4-b]pyridinone (4) and pyrazolo[3,4-b]quinolinone (6) derivatives were prepared in high yields. This novel procedure showed such advantages as environmentally benign nature, enhanced efficiency, simple operation process, and mild reaction conditions. As an application, the procedure was successfully used in the preparation of a set of pyrimidine nucleoside–pyrazolo[3,4-b]pyridine and pyrazolo[3,4-b]quinolinone hybrids with potential biological activities.     

Ft-Raman Study of Three Synthetic Solid Solutions Formed by Orthorhombic Sulfates: Celestite-Barytes,Barytes-Anglesite and Celestite-Anglesite

Abstract

In the present work, three different solid solutions whose end-members are the orthorhombic sulfates celestite (SrSO₄), barytes (BaSO₄) and anglesite (PbSO₄) are studied using FT-Raman spectroscopy. Sulfate anion symmetric internal modes have been examined in detail by means of band-shape analysis and component fitting procedures. the symmetric stretching mode v₁(A₁) changes its wavenumber position linearly with the cationic composition of the samples which further confirms the ideal character of the solid solutions studied. the corresponding full-width at half-height is strongly increased in the central components of the different solid solutions which can be understood as an effect of the positional disorder induced by random cationic substitution. Similar results are observed in the symmetric bending mode, v² (E). the study of the low frequency spectral region permits one to differentiate translational modes of the sulfate anion, which changes its wavenumber position when the alkali-earth metal ion changes from rotational modes. This permits the tentative band assignment of the anglesite rotational Raman bands at 134 and 152 cm^?1, which were previously not assigned.     

Magnetic properties of ErFe6Fa6 studied by magnetization and neutron diffraction

Neutron-diffraction experiments reveal that ErFe₆Ga₆ forms in the tetragonal ThMn₁₂-type of structure (space group I₄/mmm). The Fe sublattice orders ferromagnetically below K. The Er moments order antiparallel to the Fe moments which, below about 250 K, leads to a decrease of the total magnetization. The easy magnetization direction of ErFe₆Ga₆ is perpendicular to the c-axis in the whole temperature range. Refinement at 2 K shows that ErFe₆Ga₆ orders ferrimagnetically with Er moments of 8.5 (2) and Fe moments at the 8(j) site of 1.9 (1) and at the 8(f) site of 1.7 (1) , respectively. At room temperature, ErFe₆Ga₆ exhibits the same type of magnetic order, however with substantially lower Er moments of 1.0 (4) and Fe moments at the 8(f) site of 1.2 (2) . The Fe moments at the 8(j) site amount to 1.9 (5) /Fe. Received 24 November 1999 and Received in final form 27 March 2000     

Normal coordinate analysis and quantum chemical study of tris(p-fluorophenyl)antimony di(N-phenylglycinate) [(p-FC6H4)3Sb(O2CCH2NHC6H5)2]

A complete normal coordinate analysis was performed by two different methods: a classical Wilson’s G-F matrix method and the semi-empirical molecular orbital PM3 method, for a five coordinate tris(p-fluorophenyl)antimony di(N-phenylglycinate) [(p-FC₆H₄)₃Sb(O₂CCH₂NHC₆H₅)₂], known to be an in vitro antitumour molecule.      

阶梯化对快离子导体LixTiS2的结构与能量性质的影响

根据密度波理论建立了stage-2有序Li_xTiS₂(x=1/8,1/6,1/4,1/3,3/8,1/2)系统的晶胞模型.采用平面波赝势方法,对stage-2有序系统和stage-1有序Li_xTiS₂(x=0,1/4,1/3,1/2,2/3,3/4,1)系统进行了几何结构优化和总能量计算,并进行了对比研究.发现stage-2晶胞的参量c(d关键词： xTiS₂')" href="#">Li_xTiS₂ 阶梯结构 有序—无序相变 第一性原理计算     

纳米结构CoxFe3-xO4多孔微球的磁性及交换偏置效应研究

用乙二醇为溶剂,用三氯化铁、二氯化钴和醋酸铵为起始反应试剂,通过溶剂热反应首次合成了纳米结构Co_xFe_3-xO₄多孔微球.用X射线衍射仪(XRD)、透射电子显微镜(TEM)和扫描电子显微镜(SEM)表征样品的结构和形貌,结果表明,所制备的单分散Co_xFe_3-xO₄多孔微球为立方多晶结构,其直径约300 nm,是由约30 关键词： xFe_3-xO₄')" href="#">Co_xFe_3-xO₄ 多孔微球 磁性 交换偏置效应     

Structural Assignment of Stilbenethiols and Chalconethiols and Differentiation of Their Isomeric Derivatives by Means of 1H‐ and 13C‐NMR Spectroscopy

Abstract

The ¹H‐ and ¹³C‐NMR spectra of some substituted stilbenes and chalcones were assigned unambiguously on the basis of a combination of homo‐ (COSY) and heteronuclear (HETCOR) two‐dimensional methods, the chemical shifts, as well as spin‐coupling constants. The A_ik empirical parameters of the –O–C(S)–N(CH₃)₂, –S–C(O)–N(CH₃)₂, and –SH group were calculated to help predict the chemical shifts of substituted stilbenes, 4′‐nitrostilbenes, and chalcones. The ¹H‐ and ¹³C‐NMR spectra have been shown to be able to differentiate between the isomers of O‐stilbenyl (4, 5) and S‐stilbenyl N,N‐dimethylthiocarbamates (7, 8) as well as O‐chalconyl (6) and S‐chalconyl N,N‐dimethylthiocarbamates (9).