Cobalt‐based metal coordination polymers with 4,4′‐bipyridinyl groups: highly efficient catalysis for one‐pot synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones under solvent‐free conditions

Three new metal coordination complexes, namely [Co(BPY)₂(H₂O)₂](BPY)(BS)₂(H₂O)₄ ( 1 ), [Co(BPY)₂(H₂O)₄](ABS)₂(H₂O)₂ ( 2 ) and [Co(BPY)(H₂O)₄](MBS)₂ ( 3 ) (BPY = 4,4′‐bipyridine, BS = phenylsulfonic acid, ABS = p‐aminobenzenesulfonic acid, MBS = p‐methylbenzenesulfonic acid), were obtained under hydrothermal conditions. Complexes 1 , 2 , 3 were structurally characterized using single‐crystal X‐ray diffraction and infrared spectroscopy. All of them display low‐dimensional motifs: complex 1 displays a two‐dimensional structure; and complexes 2 and 3 exhibit a one‐dimensional tape structure. Through strong intermolecular hydrogen bonding interactions and weak packing interactions, all of them further stack to generate a three‐dimensional supramolecular architecture. Catalysts 1 , 2 , 3 were involved in the green synthesis of a variety of 3,4‐dihydropyrimidin‐2(1H)‐ones under solvent‐free conditions through Biginelli reactions. The corresponding catalytic product was obtained in quantitative yields (99%) under eco‐friendly synthesis conditions for the variety of reactions. Catalysts 1 , 2 , 3 exhibit excellent efficiency for the desired product, and their catalytic performance shows the following order: 2  >  1  ≈  3 , which can be ascribed to the hydrophobic interactions of different phenylsulfonate groups. The catalytic performance for the Biginelli reaction is not only dependent on the selected solvents, but also inversely proportional to the polarities of the solvents. Copyright © 2016 John Wiley & Sons, Ltd.     

Asymmetric Michael Addition of Aldimino Esters with Chalcones Catalyzed by Silver/Xing‐Phos: Mechanism‐Oriented Divergent Synthesis of Chiral Pyrrolines

The mechanism‐oriented reaction design for the divergent synthesis of chiral molecules from simple starting materials is highly desirable. In this work, aromatic amide‐derived nonbiarylatropisomer/silver (silver/Xing‐Phos) complex was used to catalyze the Michael addition of glycine aldimino esters to chalcones and successfully applied to the subsequent cyclocondensation to afford substituted cis‐Δ(1)‐pyrroline derivatives with up to 98 % ee. Besides the inherent performance of the chiral Ag/Xing‐Phos catalyst system, it was found that the workup of such reactions played an important role for the stereoselective construction of stereodivergent Δ(1)‐pyrrolines, in which an epimerization of the cis‐Δ(1)‐pyrrolines to the trans‐isomers during was revealed.     

Tailorable PC71BM Isomers: Using the Most Prevalent Electron Acceptor to Obtain High‐Performance Polymer Solar Cells

Despite being widely used as electron acceptor in polymer solar cells, commercially available PC₇₁BM (phenyl‐C₇₁‐butyric acid methyl ester) usually has a “random” composition of mixed regioisomers or stereoisomers. Here PC₇₁BM has been isolated into three typical isomers, α‐, β₁‐ and β₂‐PC₇₁BM, to establish the isomer‐dependent photovoltaic performance on changing the ternary composition of α‐, β₁‐ and β₂‐PC₇₁BM. Mixing the isomers in a ratio of α/β₁/β₂=8:1:1 resulted in the best power conversion efficiency (PCE) of 7.67 % for the polymer solar cells with PTB7:PC₇₁BM as photoactive layer (PTB7=poly[[4,8‐bis[(2‐ethylhexyl)oxy]benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]thieno[3,4‐b]thiophenediyl]]). The three typical PC₇₁BM isomers, even though sharing similar LUMO energy levels and light absorption, render starkly different photovoltaic performances with average‐performing PCE of 1.28–7.44 % due to diverse self‐aggregation of individual or mixed PC₇₁BM isomers in the otherwise same polymer solar cells.     

Magnetization reversal of Fe ultrathin film on Cu(100)

The magnetization reversal of Fe/Cu(100) ultrathin films grown at room temperature is investigated by using an in situ magneto-optical Kerr effect polarimeter with a magnet that can rotate in a plane of incidence. There occur spin reorientation transitions from out-of-plane to in-plane magnetizations in 8 and 12 monolayers (ML) thick iron films. The coercive fields are observed to be proportional to the reciprocal of the cosine with respect to the easy axis, suggesting that the domain-wall displacement plays a main role in the magnetization reversal process.     

受激布里渊散射相位共轭现象的二维数值模拟

 使用P.H.Hu等人[3，4]提出的计算途径，数值解了A.Flusberg等人[2]提出的零级方程。计算了布里渊池内随位置而变化的斯托克斯光强度、泵浦光强度和保真度，得到了布里渊池内几个位置上的斯托克斯光相位和强度的横向分布，并计算了泵浦光入口处的反射率和保真度。     

4英寸热氧化硅衬底上磁性隧道结的微制备

就如何在4英寸热氧化硅衬底上沉积高质量的磁性隧道结纳米多层薄膜材料和如何利用光刻方法微加工制备均匀性较好的磁性隧道结方面做了初步研究，并对磁性隧 道结的磁电性质及其工作特性进行了初步测量和讨论.利用现有的光刻设备和工艺条 件在4英寸热氧化硅衬底上直接制备出的磁性隧道结，其结电阻与面积的积 矢的绝对误差在10% 以内，隧穿磁电阻的绝对误差在7% 以内，样品的磁性隧道结性质具有较好的均匀性和一致性，可以满足研制磁随机存储器存储单元演示器件的基本要求. 关键词： 磁性隧道结 隧穿磁电阻 磁随机存储器 4英寸热氧化硅衬底     

质子化丙酮分子团簇的结构和振动光谱

用密度泛函B3LYP/ 6 3 1G(d)方法 ,对质子化丙酮分子团簇 (CH3COCH3) nH+ (n =1～ 7)弱相互作用体系进行了全自由度能量梯度优化 ,得到了该系列团簇的稳定结构及其对应的体系能量 .通过对构型的分析得出了质子化丙酮分子团簇 (CH3COCH3) nH+ (n =1～ 7)的生长规律 .计算了中性丙酮分子团簇体系的质子亲合能并总结出其变化趋势 .分析讨论了质子化团簇的红外振动光谱 ,发现质子化团簇的振动光谱普遍较中性环型团簇的振动光谱复杂 ,最强的振动峰来源于质子在溶剂壳中两个氧原子之间的振动 ,而且随着团簇尺寸的增加羰基的伸缩振动峰的数目也随之增多     

高功率双包层光纤激光器受激拉曼散射和热效应的理论研究

 受激拉曼散射和热效应会限制光纤激光器功率的提高。利用高功率光纤激光器的速率方程和热传导方程,理论研究了双端泵浦和分布泵浦下双包层光纤激光器的受激拉曼散射和热效应,得到了光纤中的泵浦光、激光和斯托克斯光的功率分布,光纤激光器的输出特性以及光纤中的温度分布。分析表明,当泵浦功率增大到一定值时,光纤激光器中出现SRS,一部分激光功率会转移给斯托克斯光,影响激光功率进一步提高;与双端泵浦方式相比,分布泵浦下光纤激光器的斜率效率和最大输出功率相差不大,但是,光纤中的温度分布被有效地降低,因此,分布泵浦方式更为有效。     

高电荷态离子126Xeq+与Ti固体表面作用的激发光谱

报道用150keV的高电荷态离子¹²⁶Xe^q+（6≤q≤30）轰击Ti固 体表面产生2 00—1000nm波段发射光谱的实验结果.结果显示，用电荷态足够高的离子作光谱激发源，无 需很强的束流强度（nA量级），便可激发起样品表面的原子和离子在可见光波段的特征谱线 .当入射离子剥离度q>q_c≈20时，Ti原子及其离子的特征谱线强度突然显著增强 ；不 同金属靶，特征谱线突然增强的q_c值不同.理论分析表明，这与q大于此临界值 后，单电子转移释放能量激发靶材料传导电子气体的表面等离激元密切相关. 关键词： 低速高电荷态离子 特征谱线 经典过垒模型 等离激元     

诱导空间非相干束匀滑技术的近区特性及改善技术

诱导空间非相干技术是面向激光驱动惯性约束核聚变的一种具有自身独特优势的束匀滑方法.然而直接使用诱导空间非相干方法将引起强烈的近区强度空间调制,这将威胁装置的运行安全,并严重限制装置的最大输出能力.这也是该方法应用于聚变级高功率激光装置的主要技术障碍之一.本文介绍了一种通过双透镜滤波系统对诱导空间非相干束匀滑技术导致的近区空间强度调制进行匀滑的技术.利用该技术可以在保留诱导空间非相干束匀滑方法的先天优势(更好的远区匀滑特性)的前提下,获得均匀、稳定的近区强度分布,从而避免高功率激光系统在使用诱导空间非相干束匀滑技术时,因为近区强度不均匀、不稳定导致的器件损伤及输出能力受限.在理论建模和数值分析的基础上,以近区调制度、软化因子和透过率为主要评价指标,对比分析了方形、圆形、高斯型等3种滤波孔在不同尺寸下的近区输出效果,最终给出了一种典型的优化结果:16×16诱导空间非相干分割数、0.8倍衍射极限宽度、方形小孔.此时近区强度分布均匀,同时保证了较好的远区匀滑效果和高的能量利用率.在此基础上,针对装置的实际应用情况,进一步分析了准直误差对近区强度分布的影响,结果表明准直误差小于0.1倍衍射极限便不会影响输出的近区质量.对诱导空间非相干束匀滑方法所得焦斑的模拟分析表明,滤波系统的加入能进一步改善焦斑的低频不均匀性.