Bis-tridentate IrIII Phosphors Bearing Two Fused Five-Six-Membered Metallacycles: A Strategy to Improved Photostability of Blue Emitters

Iridium complexes bearing chelating cyclometalates are popular choices as dopant emitters in the fabrication of organic light-emitting diodes (OLEDs). In this contribution, we report a series of blue-emitting, bis-tridentate Ir^III complexes bearing chelates with two fused five-six-membered metallacycles, which are in sharp contrast to the traditional designs of tridentate chelates that form the alternative, fused five-five metallacycles. Five Ir^III complexes, Px-21 – 23 , Cz-4 , and Cz-5 , have been synthesized that contain a coordinated dicarbene pincer chelate incorporating a methylene spacer and a dianionic chromophoric chelate possessing either a phenoxy or carbazolyl appendage to tune the coordination arrangement. All these tridentate chelates afford peripheral ligand–metal–ligand bite angles of 166–170°, which are larger than the typical bite angle of 153–155° observed for their five-five-coordinated tridentate counterparts, thereby leading to reduced geometrical distortion in the octahedral frameworks. Photophysical measurements and TD-DFT studies verified the inherent transition characteristics that give rise to high emission efficiency, and photodegradation experiments confirmed the improved stability in comparison with the benchmark fac-[Ir(ppy)₃] in degassed toluene at room temperature. Phosphorescent OLED devices were also fabricated, among which the carbazolyl-functionalized emitter Cz-5 exhibited the best performance among all the studied bis-tridentate phosphors, showing a maximum external quantum efficiency (EQE_max) of 18.7 % and CIE_x,y coordinates of (0.145, 0.218), with a slightly reduced EQE of 13.7 % at 100 cd m⁻² due to efficiency roll-off.     

Dimeric Manganese-Catalyzed Hydroarylation and Hydroalkenylation of Unsaturated Amides

An unprecedented Mn(I)-catalyzed selective hydroarylation and hydroalkenylation of unsaturated amides with commercially available organic boronic acids is reported. Alkenyl boronic acids have been successfully employed for the first time in Mn(I)-catalyzed carbon–carbon bond formation. A wide array of β-alkenylated amide products can be obtained in moderate to good yields, which offers practical access to five- and six-membered lactams. This protocol has predictable regio- and chemoselectivity, excellent functional group compatibility and ease of operation in air, representing a significant step-forward towards manganese-catalyzed C−C coupling.     

Surface of room temperature ionic liquid [bmim][PF6] studied by polarization- and experimental configuration-dependent sum frequency generation vibrational spectroscopy

Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface.     

QEPAS系统中石英音叉模态仿真计算与研究

对石英音叉增强型光声光谱(QEPAS)系统中常用的石英音叉进行了有限元模态计算，获得石英音叉前6阶振型与模态频率，认知了第4阶对称摆动振型为有效振动，利用单因素法分析了石英音叉的音臂长度l₁、音臂宽度w₁、音臂厚度t、音臂切角θ、音臂圆孔直径d及音臂圆孔高度h对低阶有效共振频率(Fre)的影响，敏感度依次为： l₁> w₁>d>θ>t>h，考虑实际设计情形，筛选出了l₁，w₁，d与h四个石英音叉设计变量，采用Box-Behnken实验设计方案与RSM(response surface methodology)方法，以Fre为函数目标，建立l₁，w₁，d与h的二次回归响应面模型，得到了参数之间的交互作用，利用Design-Expert软件对响应面模型进行设计参数反求，结果表明，在15 000 Hz≤Fre≤25 000 Hz计算区域内误差较小，基本满足QEPAS系统的计算需求，所提出的研究与设计方法具有一定通用性，可为QEPAS系统中石英音叉结构参数设计提供参考。     

Directing-Group-Free C7-Alkylations of N-Alkylindoles Mediated by Cationic Zirconium Complexes: Role of Brønsted Acid for Catalytic Manifold

Highly position selective alkylations of N-alkylindoles at C7-positions have been enabled by cationic zirconium complexes. The strategy provides a straightforward access to install alkyl groups at C7-positions of indoles without a complex directing group. Mechanistic studies provided support for the importance of Brønsted acids in the catalytic manifold.     

A New Method of Testing and Evaluating the Quality of Refined Montan Wax: Digital Color and GC Fingerprint

To establish a new method of testing and evaluating the quality of refined montan wax (RMW), digital color and GC fingerprint technology were introduced and applied. CIE Lab color mode was used to digitize the exterior colors of RMW, and the score obtained through a fitting function was also used to reflect its quality. It is shown that they were in complete accord with the human visual perception trend. The GC fingerprint was used to characterize the internal chemical information of RMW, and the composition of its internal features was reflected through the relative retention time (RRT) and relative peak area (RPA) values. It is shown that there was a high degree of similarity between the fingerprints, while certain differences also existed. This can be used to implement effective application of RMW to aspects such as quality control, adulteration identification, and origin attributions.

     

General Formation of Macro-/Mesoporous Nanoshells from Interfacial Assembly of Irregular Mesostructured Nanounits

Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition.     

溶胶-凝胶制备技术与新型催化材料Ⅲ.溶胶粒子表面修饰方法制备催化膜

提出用溶胶粒子表面修饰方法，结合溶胶凝胶技术制备无机催化膜．该方法的基本原理是利用合适的金属配合物在胶粒表面的吸附作用，经溶胶凝胶过程，将活性组分结合到无机膜中．实验测定结果表明：（ＮｉＥＤＴＡ）２－，ＶＯ－３，ＭｏＯ２－４，（Ｐｄ（ＮＨ３）４）２＋，ＰｄＣｌ２－４，ＰｔＣｌ２－６和ＲｈＣｌ３－６可用来修饰ＡｌＯＯＨ溶胶．以Ｐｄ／γＡｌ２Ｏ３催化膜的制备为例，经三次溶胶凝胶过程，可制得无裂缺的厚度为９μｍ的Ｐｄ／γＡｌ２Ｏ３催化膜，膜材料的平均孔直径为６ｎｍ，Ｐｄ被均匀地分布在膜的顶层，其平均粒径为２３ｎｍ．     

C72,La2@C72几何结构和电子性质的计算研究

采用密度泛涵理论(density functional theory,DFT)中的广义梯度近似(generally gradient approximation,GGA)对富勒烯C72和内掺金属La富勒烯La2@C72三种同分异构体的几何结构和电子结构进行研究.发现在C72的三种同分异构体中,满足独立五边形规则(isolated-pentagon-rule,IPR)的C72(D6d)结构最为稳定;在La2@C72三种同分异构体中,有着两对两两相邻五元环(twofused-pentagon)的La2@C72(#10611)结构最为稳定,而满足IPR的La2@C72(D6d)的结构变成了最不稳定结构.从能级图和态密度图分析得知,笼子稳定性的变化与La原子的原子轨道与C72原子轨道之间的杂化有关.Mulliken电荷分析得知,La2@C72(#10611)的两个La原子共转移了约3个电子给C72,并且,它们几乎分布在整个C笼上,形成的电子结构为La23+@C3-72.净自旋分析得知,La2@C72(#10611)中La原子磁性完全淬灭.