Solution Structure and Behavior of Benzophenone-based Achiral Bisphosphine Ligands in Noyori-Type Ru（Ⅱ）-Catalysts

We herein report on solution structural studies of Ru^Ⅱ catalysts （3a, 9） composed of achiral bisphosphine ligands （4, 8） and the enantiopure 1,2-diphenylethylenediamine （DPEN）. Complete chiral induction from enantiopure （R,R）-DPEN to achiral bisphosphine ligand 3a was observed in solution, with the complex adopting a single, stable and non-fluxional （even at 70 ℃） configuration. The coordination of the C=O moiety in 4 to the cationic Run center is considered to be of key importance in providing the higher thermodynamic and kinetic rotation barrier for the flexible bisphosphine ligand in the complex. The obtained enantioselectivity （91% enantiomeric excess） and sense of chiral induction in the hydrogenation of acetophenone were found to be solely dependent on the chirality of the 1,2-diamine. Consistent with the hydrogenation product, the （R,R）-DPEN induces a M-conformation （fight-handed） chirality for flexible phosphine ligand 4 in the complex, resulting in a 2,2-configuration about the Ru^Ⅱ center.     

Highly efficient chirality inducers in nematic liquid crystals: synthesis of 7,7’-disubstituted 2,2’-methylenedioxy-1,1’-binaphthyls

ABSTRACT

We report the synthesis of 7,7?-disubstituted 2,2?-methylenedioxy-1,1?-binaphthyls and demonstrate their application as chiral dopants in the nematic mixture MLC-6260 to produce highly twisted cholesteric phases. Especially mesogenic and/or polarizable groups in the 7,7?-positions of the bridged binaphthyls generate unusually high helical twisting powers.     

高压下混合卤化物钙钛矿CsPb(IxBr1–x)3纳米晶在激光诱导下的相分离行为

混合卤化物类钙钛矿具有多种优异的光电特性,如随卤素成分变化而大范围可调的带隙、高荧光量子产率等,是制备太阳能电池和发光二极管等光电材料的理想候选材料。然而,混合卤化物钙钛矿的稳定性较差,如在强光照条件下会发生相分离,这种不稳定性阻碍了它们在光电领域的广泛应用,因此,研究其相分离的内在机理和控制方法对于改善其特性以实现实际应用至关重要。针对强激光照射下具有不同组分的CsPb(I_xBr_1−x)₃纳米晶,系统研究了其激光诱导相分离随压强的变化,发现不同I/Br比例的CsPb(I_xBr_1−x)₃纳米晶具有不同的激光诱导相分离特征：x<0.1的富溴样品随着激光照射而迅速产生CsPbBr₃纯相,并实现较大的荧光量子产率增益;0.1<x<0.9溴含量较多的样品明显形成了富溴相,并产生了新的荧光峰;而x>0.9低溴含量样品则只产生荧光峰宽化,并伴随荧光强度的快速降低。将CsPb(I_xBr_1−x)₃纳米晶置于准静水压强环境中,观察到富溴样品和较多溴含量样品中的相分离随着压强的升高而迅速减缓,并在约0.1 GPa的较低压强下被极大程度地抑制,而低溴含量样品的相分离则随压强上升而增强。这些发现为理解和克服相关光电材料在强光工作环境中的应用问题提供了一种有效的解决途径。     

激光诱导金纳米棒图案化光纤SERS探针

研究了激光诱导沉积制备光纤表面增强拉曼散射(SERS)探针,并对探针的SERS性能进行检测。探讨光纤探针制备过程中金纳米棒溶液的浓度对探针灵敏度的影响。结果表明,将不同浓度的金纳米棒溶液进行激光诱导,在光纤端面会形成金纳米棒团簇和分散两种纳米结构。金纳米棒溶液的浓度、激光功率、诱导时间等因素都会对诱导沉积图案产生影响。实验利用功率为5 mW的激光进行诱导,在1.5×10^-9, 1.0×10^-9和7.5×10^-10 mol·L^-1的金纳米棒溶液中,经5 min沉积,制备出不同图案的光纤SERS探针。采用晶种法合成金纳米棒,用透射电子显微镜(TEM)观察金纳米棒形貌,并根据TEM图像分析计算了合成金纳米棒的长径比约为3.8。用扫描电子显微镜(SEM)观察金纳米棒的形貌以及激光诱导沉积后的纤维修饰端形貌,7.5×10^-10 mol·L^-1的金纳米棒溶液进行激光诱导,金纳米棒在光纤端面分布较为分散,而1.5×10^-9和1.0×10^-...     

Generalized Symmetric Polynomials and an Approximate De Finetti Representation

For probability measures on product spaces which are symmetric under permutations of coordinates, we study the rate of approximation by mixtures of product measures.