New Condensation Reaction of β-keto-δ-valerolactones, Carbon Disulfide and Alkyl Halides

β-Keto-δ-valerolactones, which were obtained by reaction of acetoacetate with aldehydes or ketones, reacted with carbon disulfide, alkyl halides and a new condensation reaction was developed. The structures of the products 3 were confirmed by ^1HNMR spectra and elemental analysis.     

Partial Wave Cross Sections for Collisions between Helium Atoms and Hydrogen Halide Molecules

The close-coupling method is utilized to calculate partial cross sections for elastic and inelastic scattering of He atoms with HX （X=F, Cl, Br） molecule based on the CCSD （T） potential energy surfaces obtained in the previous research. The calculation is performed at the incident energy of 200 me V. The rationality of our results has been confirmed by comparison with the available theoretical results. The tendency of the elastic and inelastic rotational excitation partial wave cross sections varying with the reduced mass of the three systems is obtained.     

Sequential Observation of Alkali-halide Gas Phase Clusters in High Resolution TOF-MS and Prediction of Their Structures

Alkali halide clusters are interesting model systems that can provide information about how crystal properties evolve. To study these properties, a high-resolution atmospheric pressure inlet time-of-flight mass spectrometry （APi-TOF-MS） study of the sequential sodium halides series, C1-（NaC1）n and Br-（NaBr）m, has been reported, and the viability of the APi-TOF- MS equipped with an electrospray ionization source in determining cluster compositions has been demonstrated. The isotopic patterns were well resolved, as n=4 and 7 were determined to be the magic numbers for C1-（NaC1）n clusters, which were particularly abundant in the mass spectra. A global minimum search based on density functional theory enabled basin hopping yield the most stable structures for the mentioned series. The structures exhibit several distinct motifs which can be roughly categorized as linear chain, rock salt, and hexag- onal ring. This work provides an effective way to discover and elucidate the nonstoichiometry sodium halide clusters. These clusters possess very high vertical detachment energies and are generally called as superhalogens, which play important roles in chemistry because they are widely used in the synthesis of new classes of charge-transfer salts.     

色心晶体及激光研究进展

色心激光是当前及今后固体可调谐激光领域的主要研究对象之一。该文综合评述了碱卤化物色心晶体及激光的研究发展概况，系统地探讨了色心的结构、光谱性质和色心晶体的制备，客观地分析了Ｆ型色心、Ｆ２＾＋型色心的发展、现状及主要激光性能。     

MCM-41负载硫醚钯配合物的合成及其催化芳基卤化物的羰基化性能

γ-(β-氰乙硫基)丙基三乙氧基硅烷依次用纳米介孔分子筛(MCM-41)固载、与氯化钯反应, 合成了MCM-41负载硫醚钯配合物. 该新型负载钯配合物是芳基卤化物的羰基化反应的有效催化剂, 为各种取代的N-苯基苯甲酰胺、苯甲酸丁酯的合成提供了方便实用的新途径.     

微库仑法测定固体样品中的可吸附有机卤化物

建立了一种固体样品中可吸附有机卤化物(AOX)的分析方法。通过恒温条件下的混合振荡提取固体样品中的有机卤化物,利用活性碳对有机卤化物进行富集,采用微库仑法对AOX进行检测。对比振荡吸附柱压滤法和振荡吸附抽滤法分析结果,表明柱压滤法在系统空白值、回收率和精密度方面都要优于抽滤法,其系统空白值为0.44μg(Cl-),空白加标回收率为93.8%~99.0%。利用本方法对沉积物和土壤中的AOX进行了测定。     

基于易升华添加剂辅助合成纯相富铯(CH(NH2)2)xCs1−xPbI3 钙钛矿

钙钛矿材料化学组分是决定钙钛矿太阳能电池效率和稳定性的关键,纯无机钙钛矿CsPbI₃具有相对较好的热稳定性和光稳定性,但由于Cs⁺具有较小的离子半径而导致无机钙钛矿相不稳定。最近研究发现富铯FA_xCs_1?xPbI₃钙钛矿具有相对稳定的相结构,且可以很大程度上保持无机钙钛矿材料的热稳定性和光照稳定性,是一种非常具有前景的钙钛矿材料体系。目前这种富铯的FA_xCs_1?xPbI₃材料合成是通过引入过量有机组分FAI实现的,其中FAI一方面充当钙钛矿的掺杂剂,另一方面过量的FAI充当添加剂。由于其具有较高的升华温度,后续需要较高的温度使过量的FAI升华,实际上这在实验上很难实现对FAI升华量的精确控制。本文重点研究具有低升华温度的胺类,如碘甲胺(MAI)、碘化二甲胺(DMAI)、碘化乙胺(EAI)、碘化胺(NH₄I)和醋酸甲脒(FAAC),作为添加剂制备富铯FA_xCs_1?xPbI₃钙钛矿材料体系的可行性,这一方面可以有效降低钙钛矿薄膜的热处理温度;另一方面可拓宽的制备纯相钙钛矿成分的窗口期,这对大面积制备纯相富铯FA_xCs_1?xPbI₃钙钛矿薄膜尤为重要。结果表明MAI和DMAI可以作为合成FA_xCs_1?xPbI₃钙钛矿材料的有效添加剂,其与PbI2间较强的作用力可以促进Cs₄PbI₆的形成并有效抑制δ-CsPbI₃副产物的生成。合适的升华温度可以使薄膜在保持钙钛矿相结构的同时在较低温度升华去除过量的添加剂,最终实现在相对温和的条件下制备纯相富铯FA_xCs_1?xPbI₃钙钛矿材料。     

新兴零维金属卤化物的光致发光与应用研究进展

零维(0D)金属卤化物是一类新兴的发光材料体系,它们具有独特的"主-客"体结构,即独立的阴离子金属卤化物多面体客体规则有序地分布在有机阳离子或碱金属阳离子形成的主体框架中。这种具有相对较"软"晶格的0D金属卤化物材料的发光主要源于自陷激子(Self-trapped excitons, STEs)复合,其通常呈现出宽带发射,且具有大的斯托克斯位移。通过筛选不同的及多样化构型的金属卤化物多面体,将其与合适的有机阳离子或者Cs~+等组合,可形成多种新型结构的0D金属卤化物,并实现丰富的STEs发光特性,其可调节的荧光发射不仅可以覆盖整个可见光区,还可实现单相白光或近红外发光,成为光致发光材料研究领域的一个热点和重点。基于此,本文结合本课题组在该领域的研究工作基础,首先讨论了0D金属卤化物的光致发光机理;其次,介绍了具有不同多面体构型的0D金属卤化物材料的发光特性及应用;最后,总结了0D金属卤化物目前亟待解决的关键科学问题,并对0D金属卤化物的未来发展方向进行了展望。     

水相铜/十二烷基取代酰肼-吡啶-N-氧化物催化咪唑的N-芳基化

设计合成了5种新型烷基取代酰肼-吡啶-N-氧化物,并将其作为水相铜催化含氮杂环与芳香碘代物偶联反应的配体.实验结果表明,十二烷基取代酰肼-吡啶-N-氧化物的催化效果最佳.对影响反应的其它条件,如铜源、碱、反应时间和温度等条件进行了优化,建立了最佳反应条件:CuO(10%,摩尔分数),NaOH(1 mmol),TBAB(5%,摩尔分数),L5(20%,摩尔分数),于120℃反应12 h,无需惰性气体保护.在此条件下,芳香碘代物与咪唑偶联反应的产率为60%~92%.该方法的特点是以水作为反应溶剂,长链烷基取代酰肼-吡啶-N-氧化物同时起到了铜催化剂配体和相转移催化剂的作用.