Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).     

Pentapnictogen heterocyclic monoanions: Structure,stability, and aromaticity

Inorganic planar ring-shape molecules with 4n + 2 π electrons are always the focus of experimental synthesis and theoretical research due to their potential aromaticity and stability. In this work, the whole series of five-membered heterocycle monoanions X _nY_5-n⁻ (X, Y = group 15 elements; n = 1-4) were thoroughly investigated by means of density functional theory calculations. They all have large formation energies and HOMO-LUMO gap energies, suggesting the potential thermodynamic and kinetic stability. Their aromaticities are comparable to that of typical aromatic hydrocarbons. Their thermal stabilities were firmly established by the ab initio molecular dynamics simulations. As most of them are predicted for the first time, their various spectra were simulated for experimental characterization. Furthermore, we demonstrate that these five-membered cyclic anions can be employed as η⁵-ligand to construct novel all-inorganic metallocenes, which may serve as the building blocks of low-dimensional nanomaterials.     

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.     

Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes

The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine.     

Direct Intermediate Regulation Enabled by Sulfur Containers in Working Lithium–Sulfur Batteries

Polysulfide intermediates (PSs), the liquid-phase species of active materials in lithium–sulfur (Li-S) batteries, connect the electrochemical reactions between insulative solid sulfur and lithium sulfide and are key to full exertion of the high-energy-density Li-S system. Herein, the concept of sulfur container additives is proposed for the direct modification on the PSs species. By reversible storage and release of the sulfur species, the container molecule converts small PSs into large organosulfur species. The prototype di(tri)sulfide-polyethylene glycol sulfur container is highly efficient in the reversible PS transformation to multiply affect electrochemical behaviors of sulfur cathodes in terms of liquid-species clustering, reaction kinetics, and solid deposition. The stability and capacity of Li-S cells was thereby enhanced. The sulfur container is a strategy to directly modify PSs, enlightening the precise regulation on Li-S batteries and multi-phase electrochemical systems.     

Approximate inverse computation using Frobenius inner product

Parallel preconditioners are presented for the solution of general linear systems of equations. The computation of these preconditioners is achieved by orthogonal projections related to the Frobenius inner product. So, min_M∈??∥AM?I∥ _F and matrix M₀∈?? corresponding to this minimum (?? being any vectorial subspace of ??_n(?)) are explicitly computed using accumulative formulae in order to reduce computational cost when subspace ?? is extended to another one containing it. Every step, the computation is carried out taking advantage of the previous one, what considerably reduces the amount of work. These general results are illustrated with the subspace of matrices M such that AM is symmetric. The main application is developed for the subspace of matrices with a given sparsity pattern which may be constructed iteratively by augmenting the set of non‐zero entries in each column. Finally, the effectiveness of the sparse preconditioners is illustrated with some numerical experiments. Copyright © 2002 John Wiley & Sons, Ltd.     

Isometries of the Dirichlet space among the composition operators

We show that every composition operator which is an isometry of the Dirichlet space is induced by a univalent full map of the disk into itself that fixes the origin. This is an analogue of the Hardy space result for inner functions due to Nordgren. The proof relies on the Stone-Weierstrass theorem and the Riesz representation theorem.

     

向列相液晶中空间光孤子的观测

分别以He-Ne激光器、半导体激光器和Ar⁺激光器作为光源照射液晶材料，在低光强入射的情况下均观察到了光束的自聚焦现象以及空间光孤子的形成，观察到了长度l>5mm的孤子波和多模空间光孤子，并对空间孤子的产生条件及特性进行了讨论. 关键词： 自聚焦 空间光孤子 向列相液晶