The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Notiz über Parachloraldehyd

Ohne Zusammenfassung     

Crystallographic report: catena‐Aqua(2,2′‐bipyrimidine)lithium(I) perchlorate

A lithium(I) coordination polymer has been formed from LiClO₄ and the 2,2′‐bipyrimidine (bpym) ligand in which each square pyramidal lithium(I) atom is coordinated in the basal plane by four nitrogen donor atoms derived from two bpym ligands and one water molecule at the apical position. These are connected into a layer structure via hydrogen‐bonding interactions involving the perchlorate anions. Copyright © 2004 John Wiley & Sons, Ltd.     

Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Synthesis and Characterization of Silica@Copper Core–Shell Nanoparticles: Application for Conjugate Addition Reactions

Silica@copper (SiO₂@Cu) core–shell nanoparticles were synthesized and well characterized by XRD, TEM, AFM, XPS, UV/Vis, TGA–MS, and ICP–AES techniques. The synthesized SiO₂@Cu core–shell nanoparticles were employed as catalysts for the conjugate addition of amines to α,β‐unsaturated compounds in water to obtain β‐amino carbonyl compounds in excellent yields in shorter reaction times. Furthermore, the catalyst works well for hetero‐Michael addition reactions of heteroatom nucleophiles such as thiols to α,β‐unsaturated compounds. As the reaction is performed in water, it allows for easy recycling of the catalyst with consistent activity.     

Living polymerization of styrene initiated by mercaptan/ε‐caprolactam

The bulk polymerization of styrene initiated by ?‐caprolactam (CL) and n‐dodecyl mercaptan (RSH) has been explored. This novel polymerization system shows living characteristics. For example, the molecular weight of the resulting polymers increases with conversion, and the system has the ability to form diblock copolymers and so forth. The polymer chain end contains thiol and lactam structures, which we have investigated with Fourier transform infrared, ¹H NMR, and ¹³C NMR techniques. Electron spin resonance spectra and theoretical calculations by the Hartree–Fock methods have been used to examine the mechanism. The results reveal that the initial polymerization starts from thiol via a chain‐transfer reaction, and the propagation proceeds by the insertion of a monomer between the terminal group and the intermediate structure of lactam. Finally, the polymerization kinetics have been examined. The polymerization rate varies linearly with the concentration of CL and RSH, and this confirms the mechanism. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4976–4993, 2004     

Soluble,saturated‐red‐light‐emitting poly(p‐phenylenevinylene) containing triphenylamine units and cyano groups

A conjugated poly(p‐CN‐phenylenevinylene) (PCNPV) containing both electron‐donating triphenylamine units and electron‐withdrawing cyano groups was prepared via Knoevenagel condensation in a good yield. Gel permeation chromatography suggested that the soluble polymer had a very high weight‐average molecular weight of 309,000. A bright and saturated red emission was observed under UV excitation in solution and film. Cyclic voltammetry showed that the polymer presented quasi‐reversible oxidation with a relatively low potential because of the triphenylamine unit. A single‐layer indium tin oxide/PCNPV/Mg–Ag device emitted a bright red light (633 nm). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3947–3953, 2004     

X波段六腔渡越管振荡器的高频特性研究

 从麦克斯韦方程出发，采用时域有限差分法（FDTD）和离散傅里叶变换（DFFT）相结合的方法，通过数值计算得出了六腔开放式谐振腔中前四个谐振频率和场分布，计算出的谐振频率与实验测量结果基本相同。比较了开放腔和封闭腔谐振频率，验证了TEM波吸收边界条件，并在实际编程计算中得以应用。计算结果为六腔渡越管振荡器的机理研究提供了依据。     

Quality assurance for the analytical data of micro elements in food

The micro element content of food is an important quality index due to the action of these elements on human health. In this article, we discuss how to ensure the reliability of analytical data on micro elements in order to truly represent the condition of food. Sampling, treatment of the analytical sample, selection of the analytical method, standard solution, and certified reference material, blank test, calibration of the instrument and equipment, application of the quality control chart, assessment of the final analytical result, and quality assurance system are briefly described. Received: 5 July 2001 Accepted: 19 November 2001