Tuning Magnetic Anisotropy in a Class of Co(II) Bis(hexafluoroacetylacetonate) Complexes

Tuning the magnetic anisotropy of metal ions remains highly interesting in the design of improved single‐molecule magnets (SMMs). We herein report synthetic, structural, magnetic, and computational studies of four mononuclear Co^II complexes, namely [Co(hfac)₂(MeCN)₂] ( 1 ), [Co(hfac)₂(Spy)₂] ( 2 ), [Co(hfac)₂(MBIm)₂] ( 3 ), and [Co(hfac)₂(DMF)₂] ( 4 ) (MeCN=acetonitrile, hfac=hexafluoroacetylacetone, Spy=4‐styrylpyridine, MbIm=5,6‐dimethylbenzimidazole, DMF=N,N‐dimethylformamide), with distorted octahedral geometry constructed from hexafluoroacetylacetone (hfac) and various axial ligands. By a building block approach, complexes 2 – 4 were synthesized by recrystallization of the starting material of 1 from various ligands containing solution. Magnetic and theoretical studies reveal that 1 – 4 possess large positive D values and relative small E parameters, indicating easy‐plane magnetic anisotropy with significant rhombic anisotropy in 1 – 4 . Dynamic alternative current (ac) magnetic susceptibility measurements indicate that these complexes exhibit slow magnetic relaxation under external fields, suggesting field‐induced single‐ion magnets (SIMs) of 1 – 4 . These results provide a promising platform to achieve fine tuning of magnetic anisotropy through varying the axial ligands based on Co(II) bis(hexafluoroacetylacetonate) complexes.     

Anisotropy of hole structures in oriented polycarbonate probed by two-dimensional angular correlation of annihilation radiation

Two-dimensional angular correlation of annihilation radiation (2D-ACAR) experiments have been performed on an uniaxially oriented polymer, bisphenol-A polycarbonate. The two-dimensional hole structures of unoriented and oriented polymers, determined from the momentum distributions, are found to be spherical and ellipsoidal, respectively. The average hole radii are determined to be 2.9 Å in the unoriented sample and between 2.3 and 3.8 Å in the oriented sample. Applications of the 2D-ACAR method to image the three-dimensional hole structures of polymeric materials are discussed. © 1996 John Wiley & Sons, Inc.     

理论研究电流注入对垂直腔面发射激光器多横模行为的影响

从包含时空变量的速率方程出发,针对弱折射率导引垂直腔面发射激光器(VCSELs),利用空间积分法分析了典型电注入参数对VCSELs多横模行为的影响,在不降低模型准确性的前提下提高了仿真效率。仿真结果表明,注入盘孔径和注入环越小、注入强度越低以及电流扩散越弱时,VCSELs更易实现单横模工作;反之,VCSELs高阶横模开始出现并呈现较强的模式竞争,引发了载流子空间烧孔效应,并导致基模强度降低。进一步得出,在环形注入方式下,高阶模式更容易出现且彼此间的竞争较盘形注入时强。     

Theoretical investigation of the crystallographic structure,anisotropic elastic response,and electronic properties of the major borides in Ni-based superalloys

ABSTRACT

In Ni-based superalloys, it is usually found that borides can strengthen the grain boundaries, thereby resulting in an increase in mechanical strength and high-temperature creep properties. Due to their importance and prevalence in Ni-based superalloys, this study employs first-principles methods to investigate the crystallographic structure, anisotropic elastic response, and electronic properties of the major borides, such as M₂B, M₅B₃ and M₃B₂ (M: Cr, Mo, W), respectively, which is necessary for the assessment of complex mechanical responses of Ni-based superalloys. The results demonstrate that the studied borides are all thermodynamically and mechanically stable. Among the M _x B _y binary borides analysed, Cr _x B _y exhibits the largest shear modulus, Young’s modulus, and Vicker hardness values, and these properties increase with the increase of B contents. The studied borides display nearly isotropic elastic properties except for W₅B₃ and W₃B₂. The electronic structure analysis of M _x B _y shows that the strong hybridisation between M-d and B-p orbitals leads to these borides exhibiting higher theoretical hardness, and the overlapping peaks of M-d and B-p orbitals move to a lower energy area with the increase of B contents, which leads to the increase of shear and Young’s moduli of M _x B _y . Furthermore, for M₃B₂ borides, the Cr-B bonds and Cr–Cr bonds are much stronger than the W-B & Mo-B bonds, and W-W & Mo-Mo bonds, respectively, which leads to Cr _x B _y yielding the largest values of elastic moduli.     

板结构计算模型的新发展

现代复合材料层合板具有高强和轻型的突出优点,从而在军工和民用等诸多领域发挥着重要作用。这种板结构的特点是随着纤维走向的不同,层间材料的物理-力学特性发生剧烈变化。沿板厚方向变形的梯度比较陡峭,并在层间结合面处发生强不连续,呈现zig-zag （锯齿状）现象。这导致横向剪应变在板的静态和动态响应中发生重要作用,不计横向变形的经典组合板计算模型CLPT难以适应现代多层板计算分析的需要。考虑横向剪切变形影响的板的计算模型得到重视和发展。需要指出,现有各种考虑剪切变形影响的计算模型虽然有了很大的发展,但在全面和准确性上仍然存在一定的不足,难以适应现代多层组合板横向力和物理性能多变的情况。模型预测的沿板厚方向位移和应力的变化规律难以通过严格的检验。本文提出的以比例边界有限元为基础的正交各向异性板的数值计算模型,同时可适用于各种薄板与厚板的分析,对现代复合材料层合板的分析具有特殊的优越性。所得到的板的位移、正应力和剪应力沿板厚方向的变化,与三维弹性理论的标准解高度吻合。数值算例进一步表明,随着层间纤维走向的变化,板内位移场和应力场沿板厚方向剧烈变化所呈现的锯齿现象均可以精准地进行模拟。据此,本文建议方法对现代板分析的广泛适应性和高度准确性得到了充分论证。     

荧光各向异性法均相检测酸性、中性和碱性介质中的蛋白酶

荧光各向异性;罗丹明;蛋白酶;胰蛋白酶;胃蛋白酶;菠萝蛋白酶;蛋白酶抑制剂     

超拉伸聚乙烯的弹性模量和导热性能

为了揭示聚合物分子链伸展、取向的本征特性，发展了两个新的测量方法和实验装置，用于研究拉伸比高达２００的超拉伸聚乙烯凝胶的弹性性能、传热性能和聚合物结构的关系．应用激光脉冲热致超声法给出材料拉伸方向和横向杨氏模量，应用激光脉冲光热辐射法给出拉伸方向，横向和厚度方向的导热系数．随拉伸比λ的增加，轴向杨氏模量急剧的增加，而横向的仅有少许减小．导热系数具有相似的特性．本文发现当λ＝２００时，这种拉伸取向聚乙烯的轴向模量可达钢的８０％，而导热系数甚至可达２倍，直至成为热的良导体，这是由于在高拉伸比时形成了相当数量的伸展分子链构成的针状晶体———晶桥．本文提出晶桥作为短纤维分散相的取向聚合物的结构模型，对于超拉伸聚乙烯的上述特性可以进行统一描述和定量化分析，和实验结果很好符合．     

Polarity and steric effect of the lateral substituent on the mesophase behaviour of some newly prepared liquid crystals

Eight homologous series of 2- (or 3-) substituted phenyl 4?-(4?-alkoxy phenylazo) benzoates (In_a–h) were prepared in which, within each homologous series, the length of the terminal alkoxy group varies between 6, 8, 10 and 12 carbons, while the other substituent, X, is a laterally attached polar group that alternatively changed from CH₃, H, F, Br and CN. Compounds prepared were characterised by infrared and ¹H-NMR spectroscopy, and their mesophase behaviour investigated by differential scanning calorimetry and identified by polarised light microscopy. The results were discussed in terms of polarity and steric effects. The stability of the mesophase was correlated once with the dipolar anisotropy of the whole molecule and another with the dipolar anisotropy of the substituent, X. A comparative study was made between the investigated compounds and their previously prepared linear 4-substituted isomers, namely 4-substituted phenyl 4?-(4?-alkoxy phenylazo) benzoates (In_i–k).