Crystal Structures and Photoluminescence Properties of Zinc(II) and Cadmium(II) Coordination Polymers with “Y”‐Shaped Ligands

Three Zn^II and Cd^II complexes with Y‐shaped dicarboxylate ligands, namely [Zn(L₁)(2,2′‐bpy)₂(H₂O)] · 2H₂O ( 1 ), [Zn(L₁)(bpp)(H₂O)] ( 2 ), and [Cd(L₁)(H₂O)] · H₂O ( 3 ) [H₂L₁ = N‐phenyliminodiacetic acid, 2,2′‐bpy = 2,2′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane] were synthesized and characterized by elemental analysis, IR spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 shows an hydrogen‐bonded 2D network, whereas compound 2 is an infinite 1D wavy chain structure, though O–H ··· O hydrogen‐bonded to form a 2D network. Compound 3 displays a 2D uninodal 3‐connected Shubnikov plane net with the point symbol of (4.8²). Moreover, the solid‐state such as thermal stabilities and fluorescence properties of 1 – 3 were also investigated.     

基于柱[n]芳烃(准)轮烷的研究进展

柱芳烃作为一类新型的大环主体分子,自2008年首次报道以来,引起了人们,特别是化学家的广泛关注.目前,它已在分子识别、(准)轮烷、超分子聚合物、分子弹簧、智能跨膜离子通道、囊泡、金属有机骨架结构等众多研究领域作为重要模块得到初步的应用.主要将以柱芳烃作为主体大环分子来构筑(准)轮烷的研究进展进行简要的综述,同时还介绍了基于柱芳烃的(准)聚轮烷的研究概况,并对未来的发展作了进一步展望.     

Synthesis of High Molecular Weight Cyclic Poly(ε‐caprolactone)s of Variable Ring Size Based on a Light‐Induced Ring‐Closure Approach

High molecular weight cyclic poly(ε‐caprolactone)s (cPCLs) with variable ring size are synthesized via light‐induced ring closure of α,ω‐anthracene‐terminated PCL (An‐PCL‐An). The ring size of cPCL is tunable simply by adjusting the polymer concentration from 10 to 100 mg mL⁻¹ in THF. The cyclo­addition via the bimolecular cyclization of An‐PC‐An is well characterized by a variety of analyses such as ¹H NMR and UV–vis spectroscopies, gel‐permeation chromatography, and differential scanning calorimetry. The reversible dimerization of An induced by heating enables the cyclic PCL to have a switchable “on–off” capability. This novel light‐induced ring‐closure technique can be one of the most powerful candidates for producing various well‐defined cyclic polymers in highly concentrated polymer solution.

     

Phase‐preserved macroscopic visible‐light carpet cloaking beyond two dimensions

Transformation optics, a recent geometrical design strategy of light manipulation with both ray trajectories and optical phase controlled simultaneously, promises an invisibility cloaking device that can render a macroscopic object invisible even to a scientific instrument measuring optical phase. Recent “carpet” cloaks have extended their cloaking capability to broadband frequency ranges and macroscopic scales, but they only demonstrated the recovery of ray trajectories after passing through the cloaks, while whether the optical phase would reveal their existence still remains unverified. In this paper, a phase‐preserved macroscopic visible‐light carpet cloak is demonstrated in a geometrical construction beyond two dimensions. As an extension of previous two‐dimensional (2D) macroscopic carpet cloaks, this almost‐three‐dimensional carpet cloak exhibits three‐dimensional (3D) invisibility for illumination near its center (i.e. with a limited field of view), and its ideal wide‐angle invisibility performance is preserved in multiple 2D planes intersecting in the 3D space. Optical path length is measured with a broadband pulsed‐laser interferometer, which provides unique experimental evidence on the geometrical nature of transformation optics.

     

Long-Chain Alkane Dehydrogenation over Hierarchically Porous Ti-Doped Pt–Sn–K/TiO2–Al2O3 Catalysts

Kinetics and Catalysis - Hierarchically porous γ-Al2O3, TiO2–Al2O3 composite supports, and Pt–Sn–K/Al2O3 and Pt–Sn–K/TiO2–Al2O3 catalysts were prepared...     

硼氮杂薁基[4]螺烯的设计合成及性质研究※

本工作设计合成了分别含有B—N键和C=C键的薁基[4]螺烯类分子1a/1b和2, 其中B—N键和C=C键互为等电子体. 紫外-可见吸收光谱、电化学循环伏安测试和理论计算结果表明B—N键可以调控共轭骨架的电子结构及芳香性. 单晶结构表明1a具有螺旋几何构型, 晶体中存在P和M两种对映异构体. B—N键具有部分双键性质, 硼氮六元环具有一定的芳香性. 大位阻基团2,4,6-三甲基苯基(Mes)使得1b在三氟乙酸(TFA)作用下不会发生类似于1a的脱硼化, 而是发生和2相似的可逆质子响应, B—N键对薁单元的质子响应性质无明显影响. 三配位的硼原子可以进一步和氟离子配位, 使得1a对氟离子有明显的选择性响应, 而1b则因大位阻的Mes取代基的存在对氟离子无明显的响应性. 本工作报道了新型薁基硼氮杂螺烯及全碳螺烯分子, 为薁基多环芳烃的“自下而上”合成及性质研究提供了参考.     

First-principles study of fundamental properties and electronic structure of alloys

We have performed first-principles calculations using full-potential augmented-plane-wave method to investigate the fundamental properties of the Cd_1–xZn_xTe alloys. The composition dependence of the lattice constant and the bulk modulus have been estimated from total energy calculations. By means of the analytical fitting the band structures in the vicinity of the Brillouin center a complete set of effective electron- and hole-masses have also been derived. In order to further understand the effects of the chemical bonding on the above macroscopic properties we then studied the relaxation behaviors and the changes of the electronic states upon alloying for x=0.25 system. The results presented here yield a general understanding of the fundamental properties for the Cd_1–xZn_xTe crystals studies.     

Selective adsorption behaviors of guest molecules COR in the hexamer host networks at liquid/solid interface

Here,the selective adsorption behaviors of guest molecule COR in two hexamer host grids were investigated by means of scanning tunnelling microscope(STM).The assembled structures of small functional organic molecules TTBTA and TATBA were thermodynamically stable.Interestingly,the introduction of the guest molecule COR destroyed the original hexamer structure of TTBTA and combined with it to form a new triangular host-guest system.Different from TTBTA,the introduction of the guest molecule COR did not affect the six-membered ring structure of TATBA.Furthermore,the co-assembly structure of TTBTA/TATBA/COR was established and the guest molecule COR showed preferential adsorption to the TATBA host grid.Density functional theory(DFT) calculations had been performed to disclose the mechanism of the involved assemblies.