Infrared spectra of M+NO 3 − contact ion pairs in aprotic solvents and matrix isolated in the corresponding glasses

Studies of the vibrational spectra of matrix-isolated M⁺NO ₃ ^– ion pairs have been extended to glassy aprotic solvents. The deuterated form of the solvents DMSO, THF, and ACN have windows through the 7- nitrate ionv ₃(e) mode infrared region, so it was possible to clearly observe the splitting of the degeneracy of this mode,v ₃, produced by the contacting, but solvated, alkali metal cation. Primary attention has been directed to the extent to which this splitting is reduced relative to the argon matrix values. This reduction, which reflects electron-density transfer from the solvating molecules to the ion pairs, is comparable to that observed for H₂O and NH₃ matrices as the splitting is reduced to 20–35% of the argon-matrix values. The extent of reduction ofv ₃ for the different solvents has been related to Gutmann's donicity number scale with the correlation holding well for solvent molecules of comparable size, DMSO, THF and DMF, but breaking down for the smaller linear ACN, apparently because of more molecules in the cation solvation sphere. The matrix data have also been used, through comparison with spectra for saturated liquid solutions of Li⁺NO ₃ ^– , to show that the contact ion pair is the dominant species in liquid THF and ACN, whereas the ions are largely solvent separated in DMSO.     

Tuning the optical properties of ZnTPP using carbonyl ring fusion

Zinc meso-tetraphenylporphyrin (ZnTPP) was modified in such a way to allow the effect of an asymmetric structural distortion on its optical properties to be investigated. This involved the fusion of a phenyl group to an adjacent pyrrole ring via a carbonyl bridge. With the aid of Density Functional Theory (DFT) and time-dependent DFT (TD-DFT) calculations it was found that the asymmetric distortion away from planarity induced by the carbonyl fusion resulted in a loss of degeneracy in the two lowest unoccupied molecular orbitals (LUMOs). The effect was a red shift of the electronic absorbance bands, an increased Q:B ratio from 0.046 in ZnTPP to 0.096 in the fused derivative, and the appearance of additional UV–vis peaks. This study therefore suggests that structural distortions, as well as electronic substituents may be used to alter absorbance spectra, a technique which is of interest in the design of light-harvesting dyes.     

Redox non-innocence of thioether crowns: spectroelectrochemistry and electronic structure of formal nickel(III) complexes of aza-thioether macrocycles

The Ni^II complexes [Ni([9]aneNS₂‐CH₃)₂]²⁺ ([9]aneNS₂‐CH₃=N‐methyl‐1‐aza‐4,7‐dithiacyclononane), [Ni(bis[9]aneNS₂‐C₂H₄)]²⁺ (bis[9]aneNS₂‐C₂H₄=1,2‐bis‐(1‐aza‐4,7‐dithiacyclononylethane) and [Ni([9]aneS₃)₂]²⁺ ([9]aneS₃=1,4,7‐trithiacyclononane) have been prepared and can be electrochemically and chemically oxidized to give the formal Ni^III products, which have been characterized by X‐ray crystallography, UV/Vis and multi‐frequency EPR spectroscopy. The single‐crystal X‐ray structure of [Ni^III([9]aneNS₂‐CH₃)₂](ClO₄)₆?(H₅O₂)₃ reveals an octahedral co‐ordination at the Ni centre, while the crystal structure of [Ni^III(bis[9]aneNS₂‐C₂H₄)](ClO₄)₆?(H₃O)₃? 3H₂O exhibits a more distorted co‐ordination. In the homoleptic analogue, [Ni^III([9]aneS₃)₂](ClO₄)₃, structurally characterized at 30 K, the Ni? S distances [2.249(6), 2.251(5) and 2.437(2) Å] are consistent with a Jahn–Teller distorted octahedral stereochemistry. [Ni([9]aneNS₂‐CH₃)₂](PF₆)₂ shows a one‐electron oxidation process in MeCN (0.2 M NBu₄PF₆, 293 K) at E_1/2=+1.10 V versus Fc⁺/Fc assigned to a formal Ni^III/Ni^II couple. [Ni(bis[9]aneNS₂‐C₂H₄)](PF₆)₂ exhibits a one‐electron oxidation process at E_1/2=+0.98 V and a reduction process at E_1/2=?1.25 V assigned to Ni^II/Ni^III and Ni^II/Ni^I couples, respectively. The multi‐frequency X‐, L‐, S‐, K‐band EPR spectra of the 3+ cations and their 86.2 % ⁶¹Ni‐enriched analogues were simulated. Treatment of the spin Hamiltonian parameters by perturbation theory reveals that the SOMO has 50.6 %, 42.8 % and 37.2 % Ni character in [Ni([9]aneNS₂‐CH₃)₂]³⁺, [Ni(bis[9]aneNS₂‐C₂H₄)]³⁺ and [Ni([9]aneS₃)₂]³⁺, respectively, consistent with DFT calculations, and reflecting delocalisation of charge onto the S‐thioether centres. EPR spectra for [⁶¹Ni([9]aneS₃)₂]³⁺ are consistent with a dynamic Jahn–Teller distortion in this compound.     

Structural Dependence of Magnetic and Transport Properties in Doped Manganite Perovskites

1 INTRODUCTION In recent years, ABO3-type perovskite-like manganites, RE1xDxMnO3 (RE = rare earth ions, D = Ca2+, Sr2+, Ba2+ etc.), have inspired remarkable attention due to the colossal magnetoresistance (CMR) effects for fundamental and practical consideration [1, 2]. Since A- and B-site substitution can give rise to a large number of derivant compounds, fruitful structural, magnetic and transport properties would be expected in this family. As we have known, the ideal ABO3-typ…     

Determination of the Molecular Arrangement in Liquid Crystals by Polarization of Fluorescence

Polarized luminescence intensity reading and the polarized absorbance spectra of 4-diethyl-amino-4′-nitrostilbene “impurity” in the n-butyl-p/p-hexyloxyphenyloxycarbonyl/-phenyl-carbonate liquid crystal were measured. Degrees of orientational order, S₁ and S₂, of the nematic liquid were calculated from relative values of the absorbance and luminescence intensity components. A function, which describes the angular molecular distribution with respect to a preferred direction in the liquid crystal, is plotted.     

HT-7U真空室振动时效消应力分析

针对HT-7U真空室拼焊过程中产生的焊接变形, 应用振动时效(VSR)工艺, 以消除拼焊处残余应力, 提高真空室的尺寸精度. 通过振动过程中动应力分析和VSR工艺前后残余应力的对比测量, 了解真空室拼焊处动应力和残余应力的分布状况, 实验结果表明VSR工艺消应力效果良好.     

Distortion control of conjugacies between quadratic polynomials

We use a new type of distortion control of univalent functions to give an alternative proof of Douady-Hubbard’s ray-landing theorem for quadratic Misiurewicz polynomials. The univalent maps arise from Thurston’s iterated algorithm on perturbation of such polynomials.