19F NMR and Structure of Pt (IV) Hexafluorocomplexes

The present work cites the investigation results of ¹⁹F NMR spectra in polyerystalline compounds of the Me _n[PtF₆]_m type, where Me - Li⁺, Na⁺, K⁺, Ca²⁺, Sr²⁺, Ba²⁺, La³⁺ and Ag⁺. The use of a NMR spectrometer with high field stress (～24 kOe) made possible the observation of different chemical shifts in solids of NMR signals from two nonequivalent fluorine types in octahedric complexes of [PtF₆]^2-.¹⁹ NMR and Structure of Pt (IV) Hexafluorocomplexes     

Vibrational spectra of the layered monofluorophosphate (V), NH4Ag3(PO3F)2

The powder Fourier‐transform (FT) infrared (IR) and Raman spectra of the recently characterized NH₄Ag₃(PO₃F)₂ were recorded and are discussed with a site‐symmetry analysis based on its known structural data. Some comparisons are made with the solution spectra of the PO₃F²⁻ anion and with those of crystalline Ag₂PO₃F. Copyright © 2009 John Wiley & Sons, Ltd.     

NMR line broadening in solids by slowing down of spin fluctuations

The¹⁰⁹Ag nuclear magnetic resonance line in a sample of polycrystalline AgF is observed to broaden substantially when the¹⁹F spins are irradiated near the magic angle in their rotating frame. This is due to the reduction of¹⁹F—¹⁹F dipolar coupling, which normally causes fluctuations in the¹⁹F—¹⁰⁹Ag interactions (Abragam and Winter), inducing an exchange narrowing analogous to classical motional narrowing. The¹⁰⁹Ag linewidths obtained over the entire motional range at different¹⁹F frequencies are compared with those calculated exactly from the ratio of second to fourth moment.     

Vibrational study of H3OUO2PO4 · 3 H2O (HUP) and related compounds. phase transitions and conductivity mechanisms: part I,KUO2PO4 · 3 H2O (KUP)

Infrared and Raman spectra of polycrystalline KUO₂PO₄ · 3 H₂O (KUP) and its isotopic derivatives KUO₂P¹⁸O₄ · 3 H₂O and KUO₂PO₄ · 3 D₂O have been investigated in the 4000-10-cm^?1 range at different temperatures. An assignment of the bands in terms of UO₂, PO₄ and H₂O vibrations has been proposed. Combined differential scanning calorimetry and spectroscopic data show two diffuse phase transitions near 130 and 230 K. Comparison of the vibrational spectra of phase I at 300 K and phase IV at 100 K indicates that ordering of the water molecules with subsequent ordering of PO₄ tetrahedra on a site with lower symmetry appears to be the main mechanism responsible for the phase transformation. All the six O-H distances of water molecules in phase IV are found to be crystallographically nonequivalent. Conducting ion frequencies and the corresponding force constants have been determined for the analogous compounds MUP with M = K⁺, Na⁺, Ag⁺, NH⁺₄, Tl⁺ and H₃O⁺ and compared with other properties of these ionic conductors. Conductivity mechanisms in these materials are discussed.     

Thermoelectric power of the vitreous electrolyte (AgI)0.79(Ag2O.B2O3)0.21

We have determined the thermoelectric power ? of the high ionic conductivity glass (AgI)_0.79(Ag₂O.B₂O₃)_0.21; ? is negative throughout the investigated T range, 320–500 K. The heat of transport of the mobile Ag⁺, Q_Ag, taken as the slope of the straight line fitting ? versus 1/T, is quite lower than the activation energy obtained from conductivity data, viz. Q_Ag = 2.81 kcal/mole^-1 < E_act = 4.34 kcalmole^-1. To circumvent this discrepancy, the analysis of the experimental data is carried out as follows: (i) it is supposed that Q_Ag = E_act in agreement with the free ion theory for solid electrolytes; (ii) the vibrational part of the silver ion entropy, S(Ag⁺, vib), is assumed to be equal to the entropy of silver, S(Ag); (iii) on the ground of a structural model for this kind of glasses, the ideal configurational entropy of the mobile Ag⁺, S(Ag⁺, conf)_id, is evaluated through a statistical approach. The ideal ionic entropy is defined as S(Ag⁺)_id = {S(Ag⁺, vib) + S(Ag⁺, conf)_id}; (iv) the difference {S(Ag⁺)_exp - S(Ag⁺)_id} is viewed as an excess entropy and is described according to the classical model of the regular solutions.     

Coordination and solvation of noble metal ions: Infrared spectroscopy of Ag+(H2O)n

Vibrational spectra of mass-selected Ag⁺(H₂O)_n ions are measured by infrared photodissociation spectroscopy and analyzed with the aid of density functional theory calculations. Hydrogen bonding between H₂O molecules is found to be absent for cold Ag⁺(H₂O)₃, but detected for Ag⁺(H₂O)₄ through characteristic changes in the position and intensity of OH-stretching transitions. The third H₂O coordinates directly to Ag⁺, but the fourth H₂O prefers solvation through hydrogen bonding. The preference of the tri-coordinated form is attributed to the inefficient 5s–4d hybridization in Ag⁺, in contrast to the efficient 4s–3d hybridization in Cu⁺. For Ag⁺(H₂O)₄, however, di-coordinated isomers are identified in addition to the tri-coordinated one.     

Vibrational Spectra of Ag2CrO4

It has been shown¹ recently that Ag₂CrO₄ has a crystal structure which is unique among simple anhydrous chromates studied to date. Like the chromates of potassium², rubidium³, and cesium⁴, it may be assigned to the space group Pnma - D_2h ¹⁶ with four formula units per unit cell and chromium atoms on C_s sites. However, unlike the alkali-metal chromates, the cations are equally divided between sites of C_s and C_i symmetries. Furthermore, metal-oxygen distances in Ag₂CrO₄ range from 2.34 to 2.62Å, as contrasted with 2.7 to about 3.2Å in K₂CrO₄, and point to a greater degree of convalent bonding between cations and anions.¹ The present infrared and Raman data have been obtained with an interest in determining the spectral manifestations of this unique structure.     

Ag+掺杂的立方相Y2O3:Eu纳米晶体粉末发光强度研究

采用化学自燃烧法制备了不同Ag⁺掺杂浓度的Y₂O₃:Eu纳米晶体粉末样品(［Y³⁺］∶［Eu³⁺］∶［Ag⁺］=99∶1∶X，X=0—3.5×10^-2)，以及通过退火处理得到了相应的体材料.根据X射线衍射谱确定所得纳米和体材料样品均为纯立方相.实验表明在纳米尺寸样品中随着Ag离子浓度的增加，荧光发射强度随之增加，当X=2×10^-2时达到最大值，其发光强度比X=0时提高了近50%.当Ag离子浓度继续增加，样品发光强度保持不变.在相应的体材料样品中则没有观察到此现象.通过对各样品的发射光谱，激发光谱，X射线衍射图谱，透射电镜(TEM)照片和荧光衰减曲线的研究，分析了引起纳米样品荧光强度变化的原因是由于Ag离子与表面悬键氧结合，从而使这一无辐射通道阻断，使发光中心Eu³⁺的量子效率提高；Ag⁺的引入所带来的另一个效应是使激发更为有效.这两方面原因使发光效率得到了提高.     

Studies of Hindered Rotation and Magnetic Anisotropy by 1H, 13C and 19F NMR. The Diels-Alder Adduct of N- Pentafluorophenylmaleimide and Phencyclone: A Model for Drugs.

The potent Diels-Alder diene, phencyclone, 1, reacts with N-pentafluorophenylmaleimide, 2, to form an adduct, 3, characterized by ¹H, ¹³C, and ¹⁹F NMR at 300, 75 and 282 MHz, respectively. The one-dimensional (1D) and two-dimensional (2D) ¹H and ¹³C NMR spectra of 3 at ambient temperatures imply a slow exchange limit (SEL) regime with respect to rotation of the unsubstituted bridgehead phenyl groups about severely hindered C(sp²)-C(sp³) bonds. Major non-bonded interactions are expected between the ortho protons of the C₆H₅ groups and H-1, 8 of the phenanthrenoid moiety of 3. ¹⁹F 1D and 2D (COSY) NMR spectra show that the SEL regime also obtains for rotation about the N-C₆F₅ bond of 3, with five separate fluorine signals seen, consistent with a preferred conformation in which the C₆F₅ may lie roughly perpendicular to the plane of the pyrrolidinedione moiety, and may be in the mirror symmetry plane of 3. The results are considered relevant to hindered aryl rotations in numerous Pharmaceuticals. Selected spectral data for 2 and precursors are also presented.     

1H, 13C and 19F NMR Studies of the Diels-Alder Adduct of p-Fluoranil with Phencyclone. II. Hindered Phenyl Rotations and Anisotropic Effects in a Model Compound for Drugs

Abstract

The Diels-Alder adduct of phencyclone, compound 1, with p-fluoranil, compound 3, has been prepared in refluxing toluene. The adduct, compound 2, has been examined by ¹H, ¹³C and ¹⁹F NMR spectroscopy at 300, 75 and 282 MHz, respectively. At ambient temperature, the unsubstituted bridgehead phenyl groups in adduct 2 are found to exhibit hindered rotation, resulting in slow exchange limit (SEL) ¹H NMR spectra. Full aryl proton assignments are made based on 1D and 2D (COSY45) NMR. The ¹⁹F NMR (proton coupled) reveals one of the two ¹⁹F signals to be a triplet. This resonance collapses to a singlet in the proton decoupled ¹⁹F spectrum, implying an unexpected long range ¹H-¹⁹F coupling. For the ¹³C NMR spectrum, tentative assignments are presented. Data for compound 2 as a model compound for drugs are discussed in terms of the hindered aryl rotation and evidence of magnetic anisotrppic effects.     

BF+2注入多晶硅栅F迁移特性的分析与模拟

在深入分析BF⁺₂注入多晶硅栅F在多晶硅栅中迁移特性的基础上，建立了F在多晶硅栅中的迁移方程.采用有限差分法，模拟了BF⁺₂注入多晶硅栅F在多晶硅栅中的分布.模拟结果与二次离子质谱(SIMS)分析结果相符.给出了80keV，2×10¹⁵cm^-2 BF⁺₂注入多晶硅栅900℃，30min退火条件下F在多晶硅中的发射系数e=6×10关键词：     

Semiempirical molecular orbital calculations of anisotropic 1H, 13C and 19F hyperfine coupling constants in hydrocarbon and fluorocarbon radicals

The anisotropic hyperfine coupling constants (AHCC) from the electron spin resonance (E.S.R.) spectra of a variety of atoms in organic radicals have been calculated by means of semiempirical molecular orbital wavefunctions in the INDO approximation. Hyperfine tensors involving ¹H, ¹³C and ¹⁹F nuclei are obtained for the ?H, ?H₃, CH₃?H₂, (CH₃)₃? hydrocarbon radicals, malonic acid radical, ?H₂F, ?F₂H, ?F₃ and CF₃?H₂ radicals. The calculated values are compared with available experimental, non-empirical and semiempirical values for these radicals. All integrals of the operator entering the electronic contributions have been evaluated over Slater type orbitals. The introduction of deorthogonalized wavefunctions gives generally better calculated results. In particular, the tensor components of the ¹⁹F AHCC are in good agreement with the experimental results without the necessity of readjusting the effective nuclear charges.     

Polarization and energy barriers in ferroelectric pyridinium tetrafluoroborate

Measurements of the ¹H and ¹⁹F nuclear magnetic resonance (NMR) second moments were performed for a polycrystalline sample of (PyH)BF₄, whereas the shape of the ²H NMR line was analysed for a polycrystalline sample of (d₅PyH)BF₄. Asymmetry parameter δ has been calculated for four models of pyridinium cation reorientation among inequivalent potential energy minima, using the experimental value of the ¹H NMR second moment as well as the ²H NMR line width. From knowledge of the potential shape and the population of its minima, the temperature dependence of polarization for all the models has been found. From the comparison of the experimentally determined polarization with the calculated polarization, the most appropriate model of the pyridinium cation reorientation has been chosen.     

The infra-red spectrum of 13CH3F and the general harmonic force field of methyl fluoride

Analyses of the v ₃, 2v ₃, and (predominantly) v ₁ parallel bands, and of the v ₄ and v ₆ perpendicular fundamentals have been made for ¹³CH₃F in terms of the rotational structure observed with a resolution of ～0·2 cm^-1. In addition, the band centres of the strongly Coriolis-interacting v ₂ and v ₅ fundamentals are accurately located. Some elucidation of the complex Fermi resonance interactions in the 3000 cm^-1 region is achieved through study of spectra of crystalline samples. This enables all three components of the v ₁, 2v ₂, 2v ₅ ⁰ triad to be observed for both ¹²CH₃F and ¹³CH₃F, and estimates to be made for the unperturbed vibration frequencies.

The ¹³C frequency shifts determined for all six fundamentals are used in conjunction with existing frequency, Coriolis ζ, and centrifugal distortion data for CH₃F, CD₃F, CHD₂F and CH₂DF, to determine the general harmonic force field for methyl fluoride. The extra shift data enable all 12 parameters of the force field to be fixed within narrow limits for the first time. The disagreement with predictions of the hybrid orbital model in the A₁ species can be attributed to the effect of trans repulsions arising from the fluorine lone-pair electrons, an effect which contributes to the longer CH bond in methyl fluoride compared with the other methyl halides.     

Determination of the 5d6p 3F4-5d2 3F transition probabilities of Ba I

Whether the transitions between 6s5d ³D and 5d6p ³F can be used for laser cooling of barium heavily depends upon the transition probabilities of 5d6p ³F-5d^{2 3}F. Taking the transition 6s5d ³D₃-5d6p ³F⁴ as a scale, the leakage rate of 5d6p ³F₄-5d^{2 3}F was used to evaluate the transition probabilities. 706 nm laser pulses with different durations were applied to a barium atomic beam for 6s5d ³D₃-5d^{2 3}F₄ optical pumping, and the remaining percentages in 6s5d ³D₃ were measured. After exponential fitting, the transition probability of 5d6p ³F₄-5d^{2 3}F_3,4 was determined to be 2.1(4)×10⁴ s^?1, which is in agreement with theoretical calculations using the scaled Thomas-Fermi-Dirac method.     

On-line Time Differential Perturbed Angular Correlation with Light Probe Nucleus 19F

An on-line time differential perturbed angular correlation technique has been developed with the light probe nucleus ¹⁹F. The first on-line TDPAC measurement was carried out to determine the field gradient in Cd and quadrupole moment of ¹⁹F (0.197 MeV: I ^π = 5/2⁺, T_1/2 = 89 ns). This revised version was published online in September 2006 with corrections to the Cover Date.     

A 19F NMR Study on the Interaction of the Hexafluoroanions of Group IV Elements with Cations in Solutions

In view of previous studies of tetrafluoroborate solutions¹, it appeared interesting to continue further investigations on the interactions of fluorocomplexes with different cations, in general, and of the MF₆ ^2- fluoro complexes, in particular. In this communication, the high resolution ¹⁹F NMR data are given for the aqueous and water-acetone solutions of silicon, germanium, tin and titanium hexafluorocomplexes, containing paramagnetic (Co²⁺, Ni²⁺, Cu²⁺, Cr³⁺) and diamagnetic (Be²⁺, Mg²⁺, Zn²⁺, NH₄ ⁺) cations.     

Al satellite transition spectroscopy (SATRAS) of polycrystalline aluminium borate 9Al2O3 · 2B2O3

²⁷Al NMR spectra of polycrystalline aluminium borate 9Al₂O₃ · 2B₂O₃ have been measured at 104, 130 and 156 MHz. The parameters of the quadrupole interaction and the isotropic chemical shifts have been obtained by fitting the CT/MAS pattern and consideration of the inner satellite transitions m = 3/2 ↔ 1/2 and m = −1/2 ↔ −3/2. The gain in spectral resolution concerned with the observation of the MAS lines of the inner satellites leads to complete separation of the signals of AlO₆, AlO₅ and AlO₄ polyhedra. Also signals of structural groups of one and the same coordination number can be distinguished. Experimental and theoretical lineshape calculations are compared.     

Luminescence characteristics of Dy3+ activated Na 2Sr 2Mg (BO 3)2F 2: Dy 3+ phosphor

In this paper, we have reported a new Na ₂Sr ₂Mg (BO ₃)₂F ₂:Dy ³⁺ thermoluminescence (TL) phosphor prepared via the wet chemical method. Prepared phosphor was characterized by X-ray powder diffraction, photoluminescence (PL), TL and scanning electronmicroscopy techniques. The scanning electronmicroscopic image of Na ₂Sr ₂Mg (BO ₃)₂F ₂:Dy ³⁺ phosphor confirms the micron size of particles. Under the PL study, the characteristic emission spectrum of Dy ³⁺ corresponding to ⁴F _9/2→⁶H _15/2 (481 nm) and ⁴F _9/2→⁶H _13/2 (576 nm) transitions was observed. The TL property of the as prepared phosphor was also found to be good. TL intensity of Na ₂Sr₂Mg(BO ₃)F ₂:Dy ³⁺ phosphors at 0.99 kGy exposure of γ-irradiations was compared with standard CaSO ₄:Dy phosphor. It was seen that TL intensity of Na ₂Sr ₂Mg (BO ₃)₂F ₂: Dy ³⁺ phosphors is 1.1 times less compared with the standard CaSO ₄:Dy TL dosimeter phosphor. The kinetic parameters are also discussed in detail. The values of activation energy E (eV) and frequency factor S (s ^?1) were found to be 0.57 eV and 1.25×10⁶ s^?1, respectively.     

Transmission of polar substituent effects across the cubane ring system: 19F substituent chemical shifts (SCS) of 4‐substituted (X) cub‐1‐yl fluorides revisited

¹⁹F NMR shieldings of 4‐substituted (X) cub‐1‐yl fluorides ( 4 ) for a set of substituents (X?H, NO₂, CN, NC, CF₃, COOH, F, Cl, HO, NH₂, CH₃, Si(CH₃)₃, Li, O^? and NH) covering a wide range of electronic substituent effects were calculated using the DFT‐GIAO theoretical model. The level of theory, B3LYP/6‐311+G(2d,p), provided ¹⁹F substituent chemical shifts (SCS) in good agreement with experimental values where known. By means of NBO analysis, various molecular parameters were obtained from the optimized geometries. Linear regression analysis was employed to explore the relationship between the calculated ¹⁹F SCS and polar field, resonance and group electronegativity substituent constants (σ_F, σ_R and σ_x, respectively) and also the NBO derived molecular parameters (fluorine natural charges (Q_n), electron occupancies on fluorine of lone pairs (n_F) and occupation number of the C? F antibonding orbital (σ_CF*)). The key determining parameters appear to be n_F and σ_CF*(occup). Both factors are a function of the electrostatic field influence of the substituent (σ_F effect) but are counteractive in their influence on the shifts. No evidence for a significant resonance effect influence on the shifts could be identified. Copyright © 2009 John Wiley & Sons, Ltd.