Synthesis, characterization, and catalytic activity of divalent organolanthanide complexes with new tetrahydro-2H-pyranyl-functionlized indenyl ligands

Two series of new divalent organolanthanide complexes with the general formula [η⁵:η¹-{1-R-3-(C₅H₉OCH₂)C₉H₅}]₂Ln^II (R = H, Ln = Yb (3); R = Me₃Si, Ln = Yb (4); R = H, Ln = Eu (5); R = Me₃Si, Ln = Eu (6)) were prepared by reactions of 2 equiv. of 1-R-3-(C₅H₉OCH₂)C₉H₆ (R = H (1), R = Me₃Si (2)) with the lanthanide(III) amides [(Me₃Si)₂N]₃Ln(μ-Cl)Li(THF)₃ (Ln = Yb, Eu) via a one-electron reductive elimination process. Recrystallization of 6 from n-hexane afforded [η⁵:η¹-(C₅H₉OCH₂C₉H₅SiMe₃)]₂Eu^II · (C₆H₁₄)_0.5 (7). All compounds were fully characterized by elemental analyses, and spectroscopic methods. The structures of complexes 4 and 7 were additionally determined by single-crystal X-ray analyses. The catalytic activity of the complexes on methyl methacrylate and ε-caprolactone polymerization was studied, and the temperatures, substituents on the indenyl ring, and solvents effects on the catalytic activity of the complexes were examined.     

One-pot synthesis of donor-acceptor [2]rotaxanes based on cryptand-paraquat recognition motif

Two novel cryptand-based [2]rotaxanes were synthesized by a facile one-pot reaction from three neutral precursors: easily accessible cryptand host 1 and commercially available 4,4'-bipyridine and 3,5-di-tert-butylbenzyl bromide. Their structures were confirmed by (1)H NMR, 2D NMR, HRMS and X-ray analysis. Moreover, two [2]pseudorotaxanes based on the same cryptand hosts and dibenzyl viologen guest 3 were also demonstrated both in solution and in the solid state, which are different from previously reported [3]pseudorotaxane-like complexes formed by dimethyl viologen guest 2 and the cryptands.     

Facile Preparation of Polymeric Dimers from Amphiphilic Patchy Particles

A straightforward strategy for assembling polymeric dimers from amphiphilic nanoparticles is reported. Amphiphilic polymeric nanoparticles with a mixed‐shell of PEO/P2VN blocks and a flexible core of PAA blocks are fabricated by a non‐covalent crosslinking method. Uniform polymeric dimers are efficiently and simply obtained via hydrophobic interactions under optimized conditions in selective solvent. The steric hindrance generated by reorganization of hydrophilic polymer brushes during the interparticle association is critical for morphological selectivity in the assembly. General applicability offers the possibility to organize functional NPs into superstructures with well‐defined geometry and association numbers.     

Subwavelength imaging enhancement through a three-dimensional plasmon superlens with rough surface

In this Letter we investigate the subwavelength imaging of a three-dimensional plasmon superlens based on the full vector wave simulations of optical wave propagation and transmission. The optical transfer functions are computed. Comparisons are made between the results of lenses with flat and periodic/random rough surfaces. We also study the problem of practical imaging system geometry using laser as an illumination source. Results show that the lens with periodic or random roughness can reduce the field interference effects, and provide improved focus on the transmission field and the Poynting flux. We illustrate that the subwavelength roughness in a plasmon lens can enhance the image resolution over a flat lens for both matched and unmatched permittivity conditions. The enhancement of resolution occurs because the introduced subwavelength roughness can amplify the evanescent wave components and suppress the surface plasmon resonance peaks.     

改进的K最短路径算法在通信网络中的应用

经典的K最短路径算法是最短路径算法中一个重要分支,它在交通网络的实时路径选择中起到了很重要的作用,为了将经典的K最短路径算法应用于通信网络中,我们对经典的K最短路径算法进行了改进.在求解K最大期望容量路径算法时,先对其进行权重转换,然后使用MPS算法;在求解K最大容量路径算法时,选取每个弧段源点,终点和弧段对应3个容量值最大的来进行标号;在求解K最大期望容量路径时,建立一系列的子网络,在每个子网络中先求出K最大可靠路径,对其容量进行排序,选出最小的,将大于该最小容量的所有弧集构成的网络定义为它的子网络,以此类推直到源点到目标点没有路径为止,对每个子网络中选取的K最大期望容量路径进行统一排序得到原网络中的K最大期望路径.通过网络通信实例,验证了算法的正确性和可行性.     

施工期混凝土高拱坝已灌区温度回升解析

针对施工期高拱坝已灌区温度回升的现象,结合建设中的溪洛渡特高拱坝已灌区温度回升值进行统计分析,以及将蓄水前的已灌区混凝土块近似简化为混凝土平板问题,基于混凝土天然冷却或回升理论对已灌区温度回升现象进行解析,分析表明,当前高拱坝的封拱温度低于坝址年平均气温,不可避免地出现坝址年平均气温向已灌区进行缓慢温度倒灌,而且已灌区温度回升理论值与实测温度回升值较接近,由此认为,当前施工期高拱坝已灌区温度回升,主要原因应为外界环境气温向已灌区混凝土块的温度缓慢倒灌.     

激光场线宽对四能级原子系统相干效应的影响

采用密度矩阵方程,在引入激光场线宽的条件下,计算了N型四能级原子系统中介质对探测场的吸收。结果表明:耦合场线宽的引入,消弱了四能级原子相干,对抑制吸收有增强作用,对增强吸收有抑制作用,即耦合场线宽的引入导致了退相干。控制场线宽的引入,在电磁感应透明中削弱了四能级原子相干性,降低了共振吸收,增强了光透明;在电磁感应吸收中,控制场线宽的增加使谱线中心两侧的吸收增强,削弱了谱线中心的吸收增强,从而使四能级系统的电磁感应吸收转换为电磁感应透明。     

Equivalence on some Rotfel’d type theorems

In this paper, we prove that some recent Rotfel’d theorem extensions are equivalent.     

Dinuclear Rare‐Earth Metal Alkyl Complexes Supported by Indolyl Ligands in μ‐η2:η1:η1 Hapticities and their High Catalytic Activity for Isoprene 1,4‐cis‐Polymerization

Two series of new dinuclear rare‐earth metal alkyl complexes supported by indolyl ligands in novel μ‐η²:η¹:η¹ hapticities are synthesized and characterized. Treatment of [RE(CH₂SiMe₃)₃(thf)₂] with 1 equivalent of 3‐(tBuN?CH)C₈H₅NH ( L₁ ) in THF gives the dinuclear rare‐earth metal alkyl complexes trans‐[(μ‐η²:η¹:η¹‐3‐{tBuNCH(CH₂SiMe₃)}Ind)RE(thf)(CH₂SiMe₃)]₂ (Ind=indolyl, RE=Y, Dy, or Yb) in good yields. In the process, the indole unit of L₁ is deprotonated by the metal alkyl species and the imino C?N group is transferred to the amido group by alkyl CH₂SiMe₃ insertion, affording a new dianionic ligand that bridges two metal alkyl units in μ‐η²:η¹:η¹ bonding modes, forming the dinuclear rare‐earth metal alkyl complexes. When L₁ is reduced to 3‐(tBuNHCH₂)C₈H₅NH ( L₂ ), the reaction of [Yb(CH₂SiMe₃)₃(thf)₂] with 1 equivalent of L₂ in THF, interestingly, generated the trans‐[(μ‐η²:η¹:η¹‐3‐{tBuNCH₂}Ind)Yb(thf)(CH₂SiMe₃)]₂ (major) and cis‐[(μ‐η²:η¹:η¹‐3‐{tBuNCH₂}Ind)Yb(thf)(CH₂SiMe₃)]₂ (minor) complexes. The catalytic activities of these dinuclear rare‐earth metal alkyl complexes for isoprene polymerization were investigated; the yttrium and dysprosium complexes exhibited high catalytic activities and high regio‐ and stereoselectivities for isoprene 1,4‐cis‐polymerization.     

分形图形与激光全息防伪技术

利用分形图形具有无限可分和比例尺度上的自相似的特征以及可以产生无限变量重复码的特点，通过计算机控制激光双光束干涉光刻成点阵全息光栅，从而形成数字像素全息图．构造出分形图形的迭代函数系统框架，形成丰富多彩，变化多端的分形图形，以此对点阵全息光栅编码，光刻成分形数字像素全息图．