Nature of the radical intermediates in a substituted cyclopropylcarbiny-allylcarbinyl system

We have sought to determine the nature of the free-radical precursors to ring-opened hydrocarbon 5 and ring-closed hydrocarbon 6. Reasonable alternative formulations involve the postulation of hydrogen abstraction (a) by a pair of rapidly equilibrating classical radicals (the ring-opened allylcarbinyl-type radical 3 and the ring-closed cyclopropylcarbinyl-type 4), or (b) by a nonclassical radical such as homoallylic radical 7.

[Figure not reproduced.]

Entry to the radical system is gained via degassed thermal decomposition of peresters having the ring-opened and the ring-closed structures. The ratio of 6:5 is essentially independent of the hydrogen donor concentration for decomposition of the former at 125° in the presence of triethyltin hydrdride. A deuterium labeling study showed that the α and β methylene groups in 3 (or the equivalent) are rapidly interchanged under these conditions.

Existence of two (or more) product-forming intermediates is indicated (a) by dependence of the ratio 6:5 on the tin hydride concentration for decomposition of the ring-closed perester at 10 and 35°, and (b) by formation of cage products having largely or wholly the structure (ring-opened or ring-closed) of the starting perester.

Relative rates of hydrogen abstraction by 3 could be inferred by comparison of ratios of rate constants for hydrogen abstraction and ortho-ring cyclization:

[Figure not reproduced.]

At 100° values of k_a/k_r are 0.14 for hydrogen abstraction from 1,4-cyclohexadiene and 7 for abstraction from triethyltin hydride. The ratio 6:5 at the same temperature is ~0.0035 for hydrogen abstraction from 1,4-cyclohexadiene, ~0.078 for abstraction from the tin hydride, and ≥ 5 for abstraction from cyclohexadienyl radicals. These data indicate that abstraction of hydrogen from triethyltin hydride is more rapid than from 1,4-cyclohexadiene by a factor of ~1000 for 4, but only ~50 for 3.

Measurements of product ratios at several temperatures allowed the construction of an approximate energy-level scheme. A major inference is that isomerization of 3 to 4 is exothermic by 8 ± 3 kcal/mole, in good agreement with expectations based on bond dissociation energies. Absolute rate-constant estimates are also given.

The results are nicely compatible with a classical-radical mechanism, but attempted interpretation in terms of a nonclassical radical precursor of product ratios formed even from equilibrated radical intermediates leads, it is argued, to serious difficulties.

The roles played by hydrogen abstraction from 1,4,-cyclohexadiene and from the derived cyclohexadienyl radicals were probed by fitting observed ratios of 6:5 and 5:10 in the sense of least-squares to expressions derived for a complex mechanistic scheme. Some 30 to 40 measurements on each product ratio, obtained under a variety of experimental conditions, could be fit with an average deviation of ~6%. Significant systematic deviations were found, but these could largely be redressed by assuming (a) that the rate constant for reaction of 4 with cyclohexadienyl radical is inversely proportional to the viscosity of the medium (i.e., is diffusion-controlled), and (b) that k_a/k_r for hydrogen abstraction from 1,4-cyclohexadiene depends slightly on the composition of the medium. An average deviation of 4.4% was thereby attained.

Degassed thermal decomposition of the ring-opened perester in the presence of the triethyltin hydride occurs primarily by attack on perester of triethyltin radicals, presumably at the –O-O- bond, even at 0.01 M tin hydride at 100 and 125°. Tin ester and tin ether are apparently formed in closely similar amounts under these conditions, but the tin ester predominates at room temperature in the companion air-induced decomposition, indicating that attack on perester to give the tin ether requires an activation energy approximately 5 kcal/mole in excess of that for the formation of tin ester.

Dynamic phase-mapping of domain nucleation on MgO : LiNbO3 crystal by digital holographic interferometry

The quantitative phase-mapping of the domain nucleation in MgO:LiNbO3 crystals is presented by using the digital holographic interferometry. An unexpected peak phase at the beginning of the domain nucleation is observed and it is lowered as the spreading of the domain nucleus. The existence of the nucleus changes the moving speed of the domain wall by pinning it for 3s. Such in-situ quantitative analysis of the domain nucleation process is a key to optimizing domain structure fabrication.

Optimal recording wavelength for nonvolatile photorefractive holograms in Ce : Cu : LiNbO

Three wavelengths of red, green and blue of recording beams are systemically tested for the UV-assistant recording and optical fixing of holograms in a strongly oxidized Ce:Cu:LiNbO3 crystal. Three different photorefractive phenomena are observed. It is shown that the green beams will optimally generate a critical strong nonvolatile hologram with quick sensitivity and the optimal switching technique could be jointly used to obtain a nearly 100% high diffraction. Theoretical verification is given, and a prescription on the doping densities and on the oxidation/reduction states of the material to match a defined recording wavelength for high diffraction is suggested.

Three-dimensional coupled wave study for finite-sized anisotropic volume holographic gratings under ultrashort pulsed beam readout

The three-dimensional coupled wave theory is extended to systematically investigate the diffraction properties of finite-sized anisotropic volume holographic gratings (VHGs) under ultrashort pulsed beam (UPB) readout. The effects of the grating geometrical size and the polarizations of the recording and readout beams on the diffraction properties are presented, in particular under the influence of grating material dispersion. The wavelength selectivity of the finite-sized VHG is analyzed. The wavelength selectivity determines the intensity distributions of the transmitted and diffracted pulsed beams along the output face of the VHG. The distortion and widening of the diffracted pulsed beams are different for different points on the output face, as is numerically shown for a VHG recorded in a LiNbO3 crystal. The beam quality is analyzed, and the variations of the total diffraction efficiency are shown in relation to the geometrical size of the grating and the temporal width of the readout UPB. In addition, the diffraction properties of the finite-sized and one-dimensional VHG for pulsed and continuous-wave readout are compared. The study shows the potential application of VHGs in controlling spatial and temporal features of UPBs simultaneously. (C) 2007 Optical Society of America

Wavelength dependence of light-induced domain nucleation in MgO-doped congruent LiNbO3 crystal

Within the wavelength range from 351 to 799 nm, the different reductions of nucleation field induced by the focused continuous laser irradiation are achieved in the 5 mol % MgO-doped congruent LiNbO3 crystals. The reduction proportion increases exponentially with decreasing irradiation wavelength and decreases exponentially with increasing irradiation wavelength. At one given wavelength, the reduction proportion increases exponentially with increasing irradiation intensity. An assumption is proposed that the reduction of nucleation field is directly related to the defect structure of crystal lattice generated by the complex coaction of incident irradiation field and external electric field. (c) 2007 American Institute of Physics.

Design, Synthesis, and Study of Novel Platforms for Iron-N2 Chemistry and Photoinduced, Copper-mediated C-N Bond Formation

Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CP^iPr₃) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the C_alkyl anchor in three structurally characterized oxidation states. Fe-C_alkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-C_alkyl interaction. The anionic (CP^iPr₃)FeN₂^- species can be functionalized by a silyl electrophile to generate (CP^iPr₃)Fe-N₂SiR₃. This species also functions as a modest catalyst for the reduction of N₂ to NH₃. Next, we introduce a new binucleating ligand scaffold that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N₂-Fe(μ-SAr)Fe-N₂) across at least three oxidation states (Fe^IIFe^II, Fe^IIFe^I, and Fe^IFe^I). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N₂ and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N₂-Fe(μ-SAr)Fe-N₂) system undergoes reduction of the bound N₂ to produce NH₃ (~50% yield) and can efficiently catalyze the disproportionation of N₂H₄ to NH₃ and N₂. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiP^NMe₃] and [SiP^iPr₂P^NMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH₃ and N₂H₄). Cation binding is also facilitated in anionic Fe(0)-N₂ complexes. While Fe-N₂ complexes of a related ligand ([SiP^iPr₃]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.

Additionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)₃P)₂Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic C_alkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)₂]^- and [Cu(carbazolide)₃]^- species as intermediates in these reactions.

Finally, we report a series of four-coordinate, pseudotetrahedral P₃Fe^II-X complexes supported by tris(phosphine)borate ([PhBP₃Fe^R]^-) and phosphiniminato X-type ligands (-N=PR'₃) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.

Bicyclo[3.2.0]hepta-1,4,6-triene: synthesis, thermal rearrangement, and anion formation

In order to determine the properties of the bicycloheptatrienyl anion (Ia) (predicted to be conjugatively stabilized by Hückel Molecular Orbital Theory) the neutral precursor, bicyclo[3. 2. 0] hepta-1, 4, 6-triene (I) was prepared by the following route.

Reaction of I with potassium-t-butoxide, potassium, or lithium dicyclohexylamide gave anion Ia in very low yield. Reprotonation of I was found to occur solely at the 1 or 5 position to give triene II, isolated as to its dimers.

A study of the acidity of I and of other conjugated hydrocarbons by means of ion cyclotron resonance spectroscopy resulted in determination of the following order of relative acidities:

H₂S ˃ C₅H₆ ˃ CH₃NO₂ ˃ 1, 4- C₅H₈ ˃ I ˃ C₂H₅OH ˃ H₂O; cyclo-C₇H₈ ˃ C₂ H₅OH; фCH₃ ˃ CH₃OH

In addition, limits for the proton affinities of the conjugate bases were determined:

350 kcal/mole ˂ PA(C₅ H₅^-) ˂ 360 kcal/mole

362 kcal/mole ˂ PA(C₅H₇^-, Ia, cyclo-C₇H₇^-) ˂ 377 kcal/mole PA(фCH₂^-) ˂ 385 kcal/mole

Gas phase kinetics of the trans-XVIII to I transformation gave the following activation parameters: E_a = 43.0 kcal/mole, log A = 15.53 and ∆S^ǂ (220°) = 9.6 cu. The results were interpreted as indicating initial 1,2 bond cleavage to give the 1,3-diradical which closed to I. Similar studies on cis-XVIII gave results consistent with a surface component to the reaction (E_a = 22.7 kcal/mole; log A = 9.23, ∆S^ǂ (119°) = -18.9 eu).

The low pressure (0.01 to 1 torr) pyrolysis of trans-XVIII gave in addition to I, fulvenallene (LV), ethynylcyclopentadiene (LVI) and heptafulvalene (LVII). The relative ratios of the C₇H₆ isomers were found to be dependent upon temperature and pressure, higher relative pressure and lower temperatures favoring formation of I. The results were found to be consistent with the intermediacy of vibrationally excited I and subsequent reaction to give LV and LVI.

LiMn2-xGexO4 como material catódico para baterías de ión-litio

32 p.

Judd-Ofelt intensity parameters of Er3+ doped mixed alkali aluminophosphate glasses

Lithium sodium mixed alkali aluminophosphate glasses of the composition xNa(2)O-(15-x)Li2O-4B(2)O(3)-11Al(2)O(3)-5BaO-65P(2)O(5) (where x=0, 3.75, 7.5, 11.25 and 15 mol%) containing 0.5 mol% Er2O3 were prepared by melt quenching. The absorption spectra of Er3+ were studied from the experimental oscillator strengths and the Judd-Ofelt intensity parameters were obtained. The variations of Judd-Ofelt intensity parameters (Omega(2), Omega(4) and Omega(6)), experimental oscillator strengths of certain excited states of Er3+ and hypersensitive band positions with different mixed alkali content have been discussed in detail. It was found that there were similar effects of mixed alkali on both Judd-Ofelt intensity parameter 02 and the experimental oscillator strength of the hypersensitive transition, I-4(15/2) -> H-2(11/2). No shifts in the peak wavelength of the studied transitions were found in different glasses. (c) 2006 Elsevier B.V. All rights reserved.

Ag~+-Li~+离子交换制作Er~(3+)/Yb~(3+)共掺磷酸盐玻璃平面光波导(英文)

制备了化学稳定的Er^3＋／Yb^3＋共掺的磷酸盐玻璃，并在其中制作了用于光放大器和激光器的平面光波导．这种磷酸盐玻璃的失重速率为4．7×10^-5g·cm^-2·hr^-1，小于Kigre公司商业化的磷酸盐玻璃QX／Er的失重速率．采用Ag^＋-Li^＋交换技术制作了平面光波导并用m-线光谱在632．8nm测量了平面光波导的有效折射率．根据反WKB法得到折射率形貌，计算了离子交换参数如：离子交换深度、表面折射率，折射率改变和扩散系数等．

Helmholtz Fermi surface harmonics: an efficient approach for treating anisotropic problems involving Fermi surface integrals

We present a new efficient numerical approach for representing anisotropic physical quantities and/or matrix elements defined on the Fermi surface (FS) of metallic materials. The method introduces a set of numerically calculated generalized orthonormal functions which are the solutions of the Helmholtz equation defined on the FS. Noteworthy, many properties of our proposed basis set are also shared by the FS harmonics introduced by Philip B Allen (1976 Phys. Rev. B 13 1416), proposed to be constructed as polynomials of the cartesian components of the electronic velocity. The main motivation of both approaches is identical, to handle anisotropic problems efficiently. However, in our approach the basis set is defined as the eigenfunctions of a differential operator and several desirable properties are introduced by construction. The method is demonstrated to be very robust in handling problems with any crystal structure or topology of the FS, and the periodicity of the reciprocal space is treated as a boundary condition for our Helmholtz equation. We illustrate the method by analysing the free-electron-like lithium (Li), sodium (Na), copper (Cu), lead (Pb), tungsten (W) and magnesium diboride (MgB2)

不同退火气氛下γ-LiAlO2形貌和结构研究

研究了温度梯度法生长的γ-LiAlO2晶体在1100℃下富Li气氛和空气中退火处理后的表面形貌、表面结构以及吸收光谱。发现γ-LiAlO2晶体的抛光面在1100℃空气中退火后变为粗糙面，X射线衍射(XRD)分析表明此粗糙面为单相的LiAl5O8。而γ-LiAlO2晶体的抛光面在1100℃富Li气氛中处理后几乎没有变化。同时对不同气氛下热处理的γ-LiAlO2晶体进行了光谱分析，确认了晶片中196nm的吸收峰是由Li空位引起的。

新型衬底材料γ-LiAlO2热稳定性研究

研究了温度梯度法生长的γ-LiAlO2晶体在1100℃不同气氛处理的热稳定性。借助扫描电子显微镜和X射线衍射分析发现：1100℃／10h真空和空气处理后的样品表面分别形成了均匀微孔状和岛状LiAl5O8多晶；而富Li气氛处理后样品表面仍然光滑且仍为LiAlO2。用Leitz大视场显微镜观察重新抛光后样品内部宏观缺陷，发现空气和真空处理后样品缺陷增多，分别为岛状和条纹状缺陷；而富Li气氛处理后样品中缺陷明显减少。对比不同气氛处理的4块样品吸收光谱，确认了真空和空气处理产生的196nm吸收峰可能是Li空位吸收

大尺寸高质量γ-LiAlO2晶体的制备研究

采用提拉法快速（6mm／h）生长了透明、φ45mm×50mm完整的铝酸锂晶体，但晶体中下部出现了一个树状、乳白色的核芯．分别从透明和乳白色核芯部位取样，研磨作粉末X射线衍射测试，发现两个样品所有的衍射峰均可以用γ-LiAlO2指标化．双晶摇摆曲线显示晶体透明和乳白色部位的半高宽分别为116．9arcsec和132．0axcsec，结晶质量较差．通过三步气相传输平衡法（简称VTE）处理后，透明部位半高宽值（FWHM）降至44．2arcsec，乳白色部位FWHM值降至53．3arcsec．结合快速生长和VTE

Structural, optical and electrical properties of ZnO films grown on c-plane sapphire and (100)gamma-LiAlO2 by pulse laser deposition

ZnO thin films were grown on single-crystal gamma-LiAlO2 (LAO) and sapphire (0001) substrate by pulsed laser deposition (PLD). The structural, optical and electrical properties of ZnO films were investigated. The results show that LAO is more suitable for fabricating ZnO films than sapphire substrate and the highest-quality ZnO film was attained on LAO at the substrate temperature of 550 degrees C. However, when the substrate temperature rises to 700 degrees C, lithium would diffuse from the substrate (LAO) into ZnO film which makes ZnO film on LAO becomes polycrystalline without preferred orientation, the stress in ZnO film increases dominantly and the resistivity of the film decreases exponentially. (c) 2005 Elsevier B.V. All rights reserved.