Calcium-based coordination polymers from a solvothermal synthesis of HKUST-1 in 3D printed autoclaves

A mixed-metal 1D coordination polymer [CaCu(HBTC)₂(H2O)₈]_n (where H₃BTC – benzene-1,3,5-tric arboxylic acid) was obtained in a solvothermal synthesis of a well-known copper-containing metal–organic framework [Cu₃(BTC)₂(H₂O)₃]_n (HKUST-1) in autoclaves 3D-printed from commercial polypropylene. This material was a source of calcium ions, apparently, leaking from a colorant (calcium carbonate) promoted by glacial acetic acid as a modulator used to produce large single crystals of HKUST-1. This finding was confirmed by elemental analysis and a model experiment that resulted in a new calcium-based 1D coordination polymer [Ca(H₂BTC)₂(H₂O)₅]_n under the same solvothermal conditions with no copper or calcium salts put into a 3D-printed autoclave.     

Multifunctional material Bi4Ge3O12: thermodynamic properties

Thermodynamic characteristics of a single crystal of bismuth orthogermanate (Bi₄Ge₃O₁₂), which are necessary to improve device portfolio, have been studied. It has been shown that bismuth orthogermanate is thermodynamically stable against decomposition into binary oxides at 50 °C, which gives us grounds to consider this compound promising for various applications.     

基于分子工程的方法设计首例具有Sr2Be2B2O7 (SBBO)结构的深紫外氟碳酸盐双折射晶体AMgLi2(CO3)2F (A=K,Rb)※

分子结构设计是开发新化合物和通过原子尺度操纵优化晶体结构的一种引人注目的策略. 在这个工作中, 利用分子工程的思想, 基于SBBO结构, 成功设计并合成两个新型氟碳酸盐KMgLi₂(CO₃)₂F和RbMgLi₂(CO₃)₂F. 在两个结构中, a-b平面是由CO₃和LiO₃F阴离子基团组成的无限[Li₃C₃O₆F₃]_∞层, 进一步相邻的层通过F原子连接形成一个独特的[Li₆C₆O₁₂F₃]_∞双层. 这种结构特征对改善晶体的层状生长习性和消除晶体的多晶性有很大的帮助. 光学测试表明, 该系列晶体具有大的双折射和短的紫外截止边, 是深紫外双折射晶体良好的候选材料.     

Reversible and Stepwise Single-Crystal-to-Single-Crystal Transformation of a Platinum(II) Complex with Vapochromic Luminescence

The vapochromic single-crystal-to-single-crystal (SCSC) transformation of a highly luminescent Pt^II complex bearing an N-heterocyclic carbene [Pt(CN)₂(tBu-impy)] (tBu-impyH⁺=1-tert-butyl-3-(2-pyridyl)-1H-imidazolium) is reported. The trihydrate form of the complex, which exhibits blue ³MMLCT emission owing to weak Pt⋅⋅⋅Pt interactions, changed its luminescence color from blue to yellowish-green upon the desorption of water molecules while keeping the high emission quantum yield of more than 0.45. Variable-temperature and continuous in-situ tracking of single-crystal X-ray diffraction measurements revealed that the SCSC transformation proceeds reversibly by the release and reabsorption of water molecules, thereby changing the stacked structure slightly. As a result, the dynamics of vapor-induced SCSC transformation were elucidated: that the anhydrous form returned to the original trihydrate form in a two-step process under a water vapor atmosphere. In addition, the Pt^II complex exhibited a similar SCSC response accompanied by a luminescence color change in the presence of methanol vapor, while being inactive toward ethanol vapor.     

Synthesis and crystal structures of novel glycoluril carboxylic acids conglomerates

The two novel conglomerates were obtained by crystallization of racemic (2'S,3aS,6aR)/(2'R,3aR,6aS) (glycoluril-1-yl)-3-methylbutanoic acid and (2'R,3aR,6aR)/(2'S,3aS,6aS) (4,6-dimethylglycoluril-1-yl)pentanoic acid synthesized by highly diastereoselective condensation of 4,5-dihydroxy- imidazolidin-2-ones with racemic ureido acids. The differences in the molecular geometry of synthesized racemates were studied by X-ray diffraction that showed them to crystallize as conglomerates in non-centrosymmetric space groups Pna2₁ and P2₁2₁2₁, respectively     

Mixed Fano-SP resonant absorption of THz electromagnetic waves in a photonic resonator contacting with a metal film

In terahertz frequency region, we have investigated theoretically the correlation between spectra of a free photonic structure and that deposited on a metal for several models of metal. It was found that for quasi-normal incidence of p-polarized electromagnetic field the presence of metal generates narrow spectral wells in the middle of reflection windows existing in a free photonic crystal. Quite another manifestation of metal-resonator inter-influence takes place at incident angles exceeding the Brewster angle when reflection spikes coincide with modes of photonic crystal resonator and they are absent throughout the stopband areas. The effects are strongly depended on polarization, number of periods and angle of incidence.     

Nd∶YVO4/Nd∶GdVO4双波长激光器的功率均衡实验研究

实验研究了Nd∶YVO4/Nd∶GdVO4双波长激光器在不同抽运功率条件下,通过调节热沉温度达到功率均衡时的输出特性.实验结果表明:对于Nd∶YVO4/Nd∶GdVO4双波长激光器,当提高抽运功率,需要重新降低热沉温度达到功率均衡输出,降温幅度与抽运功率增加之比为11.23℃/W.与此同时,随着抽运功率和热沉温度的变化,双波长激光器的中心波长会出现小幅度的漂移,左峰波长随抽运功率增加的蓝移速率为0.056 nm/W,右峰波长随抽运功率增加的蓝移速率为0.054 nm/W.实验还发现功率均衡条件下激光器的输出总功率随抽运功率的增加而增加,拟合斜效率为8.7%,当抽运功率为5.58 W时,输出最大总功率达到115.7 mW.     

高温、高压、高应变速率动态过程晶体塑性有限元理论模型及其应用

对于高温、高压、高应变速率加载条件下的材料冲击变形行为,动态晶体塑性模型能够直接反映晶体中塑性滑移的各向异性及其对温度、压力和微观组织结构的依赖性,因而广泛应用于材料的动态冲击力学响应、微观结构演化以及动态损伤破坏的模拟。本文综述了高压冲击下动态晶体塑性有限元的理论模型,主要包括变形运动学、包含状态方程的超弹性本构模型和晶体塑性本构模型,涉及位错滑移、相变、孪生等塑性变形机制,以及层裂、绝热剪切带等动态破坏方式。     

SU-8光栅结构中的液晶激光特性

设计制作了SU-8光栅结构的染料掺杂手性向列相液晶激光器件,在器件正面和侧面均实现了随机激光辐射。将激光染料PM597、手性剂S-811、向列性液晶TEB30A按一定比例均匀混合,注入反平行摩擦处理的液晶盒中,器件的下基板通过光掩模法刻蚀出周期为15μm的光栅。利用532 nm的Nd∶YAG固体脉冲激光器作为泵浦源,器件的侧面既在580~590 nm范围内出现了多个离散分立的随机激光辐射峰,FWHM约0.19 nm,又在579~585 nm范围内出现独立的两个激光辐射峰,FWHM约0.19 nm;在器件正面获得了584~590 nm范围的随机激光辐射谱,FWHM约0.17 nm。加热器件至61℃,液晶相变为各向同性态,器件侧面仍出现了波长约590.60 nm、FWHM约0.24 nm的激光辐射峰。分析得出,液晶盒中引入SU-8光栅结构后,光子同时在液晶分子间多重散射和SU-8光栅中布拉格反射获得反馈放大,两种机制相辅相成。器件侧面出现的独立激光辐射峰主要由SU-8光栅布拉格反射提供反馈放大形成,而器件侧面和正面的随机激光辐射峰主要由液晶分子间多重散射提供反馈放大形成。