表面荷载作用下半无限层状介质中的裂纹分析

分析了半无限层状介质中的正方形裂纹。层状材料的层面互相平行,外部荷载作用在边界面上,正方形裂纹平行于层面。基于Yue基本解的数值方法和线弹性断裂力学叠加原理,首先采用一种数值方法获得无裂纹半无限层状介质的应力场,然后将计算得到的应力按叠加原理施加在裂纹面上,并采用另一种数值方法计算此情形下裂纹面的间断位移,最后采用裂纹面的间断位移计算应力强度因子。结果显示:I型和II型应力强度因子的变化与裂纹所处的位置关系密切;层状介质中的裂纹张开和滑移受到不同介质存在的影响,进而影响到裂纹的应力强度因子。建议的数值方法可用于分析复杂荷载作用下层状介质中裂纹的断裂力学特性。     

Synthesis,Characterization and Luminescent Properties of Two Copper(Ⅰ) Complexes Based on 2,2?-Biquinoline and Phosphorous Ligand

Three new copper(Ⅰ) complexes, namely [Cu(DPEphos)(Biq)]CF_3SO_3(1) and [Cu(PPh_3)_2(Biq)]CF_3SO_3(2) and [Cu(PPh_3)_2(Biq)]ClO_4(3)(DPEphos = bis[2-(diphenylphosp hino)phenyl]ether, PPh_3 = triphenylphosphine and Biq = 2,2?-biquinoline), are synthesized and characterized by IR, ~1H NMR, ~(31) P NMR, fluorescence spectra and terahertz time-domain spectroscopy(THz-TDS). Complex 1 crystallizes in triclinic, space group P1 with a = 12.6997(5), b = 13.2813(5), c = 15.3593(6) ?, α = 80.211(3)°, β = 88.752(3)°, γ = 70.113(3)°, V = 2398.85(15) ?~3, C_(55)H_(41.2)CuF_3N_2O_(4.6)P_2S, Mr = 1018.27, Z = 2, Dc = 1.410 g/cm3, F(000) = 1048, μ = 0.628 mm-1, the final R = 0.0450 and w R = 0.1105 for 9419 observed reflections(I 2σ(I)). Complex 2 crystallizes in monoclinic, space group C2/c with a = 19.9961(7), b = 15.9774(5), c = 17.7908(6) ?, β = 119.758(4)°, V = 4982.8(3) ?~3, C_(56.47)H_(47.88)CuF_3N_2O_(4.47)P_2S, Mr = 1040.54, Z = 4, Dc = 1.387 g/cm~3, F(000) = 2154, μ = 0.606 mm-1, the final R = 0.0430 and w R = 0.1218 for 4897 observed reflections(I 2σ(I)). Complex 3 crystallizes in monoclinic, space group C2/c with a = 19.7534(8), b = 15.0797(5), c = 17.8097(7) ?, β = 116.400(5)°, V = 4751.8(3) ?~3, C_(56)H_(45)ClCuN_3O_4P_2, Mr = 984.88, Z = 4, Dc = 1.377 g/cm~3, F(000) = 2040, μ = 0.635 mm-1, the final R = 0.0731 and w R = 0.2180 for 4670 observed reflections(I 2σ(I)). In the emission spectra, shifts of emission peak are derived from ligand-centered(π-π*) transition.     

两个二亚胺及双膦配体混配铜(Ⅰ)配合物的合成、结构与太赫兹光谱

在甲醇和二氯甲烷混合溶液中制备了2个二亚胺、双膦配体混配的铜（Ⅰ）配合物[Cu₂（Dpq）₂（dppBz）₂]（SCN）₂·0.5Dpq·3CH₃OH（1）和[Cu₂（Dppz）₂（dppb）₂]（BF₄）₂·2CH₃OH·2H₂O（2）（Dppz=二吡啶[3,2-a∶2'',3''-c]并吩嗪,Dpq=吡嗪并[2,3-f][1,10]菲咯啉,dppBz=1,2-双（二苯基磷基）苯,dppb=1,4-双（二苯膦基）丁烷）,通过X射线单晶衍射确定了配合物的精确结构,并使用元素分析、核磁共振氢谱、红外光谱、紫外可见吸收光谱、荧光光谱、太赫兹时域光谱（THz-TDS）对配合物进行了表征。1的晶胞中包含2个独立的金属中心,还含有0.5个未配位的Dpq分子,类似结构较为少见;而2为通过双膦配体桥联形成新颖的双核结构。通过弱相互作用力分析可知1为三维立体堆积结构,结构中含有独特的C-S…π作用;2通过C-H…π及π…π作用形成一维无限链,大量弱相互作用的存在使配合物更加稳定。发射光谱表明配合物1在578 nm处有较强的发射,而2在547 nm有绿光发射。配合物2的THz-TDS图中在1.2 THz处的尖锐峰是由C-H…F弱相互作用引起的。