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.     

Identifying aspirin polymorphs from combined DFT-based crystal structure prediction and solid-state NMR

A combined experimental and computational approach was used to distinguish between different polymorphs of the pharmaceutical drug aspirin. This method involves the use of ab initio random structure searching (AIRSS), a density functional theory (DFT)-based crystal structure prediction method for the high-accuracy prediction of polymorphic structures, with DFT calculations of nuclear magnetic resonance (NMR) parameters and solid-state NMR experiments at natural abundance. AIRSS was used to predict the crystal structures of form-I and form-II of aspirin. The root-mean-square deviation between experimental and calculated ¹H chemical shifts was used to identify form-I as the polymorph present in the experimental sample, the selection being successful despite the large similarities between the molecular environments in the crystals of the two polymorphs.     

A Switch in the Hydrophobic/Hydrophilic Gas-Adsorption Character of Prussian Blue Analogues: An Affinity Control for Smart Gas Sorption

Porous coordination polymers are molecule-based materials presenting a high degree of tunability, which offer many advantages for targeted applications over conventional inorganic materials. This work demonstrates that the hydrophilic/hydrophobic character of Prussian blue analogues having a lipophilic feature may be tuned to optimize the gas adsorption properties. The role of the coordinatively unsaturated metal sites is emphasized through a combination of theoretical and experimental study of water, ethanol, and n-hexane adsorption.     

Banach空间二阶非线性微分方程的弱Carathéodory解

本文定义了二阶微分方程的弱 Carathéodory解 ,在不涉及紧型条件的情形下 ,直接用迭代法证明了 Banach空间二阶非线性常微分方程两点边值问题存在唯一解 ,并给出逼近解迭代序列的误差估计 ,对周期边值问题得到类似的结果     

β-MnO2高压相的从头计算模拟

 基于密度泛函理论（DFT），用完全势能线性缀加平面波方法（FPLAPW）计算模拟了MnO₂的同质多相变体（金红石型结构、CaCl₂型结构、黄铁矿型结构），通过计算，预测了β-MnO₂在5 GPa时从金红石型结构转变为CaCl₂型结构，在20 GPa时进一步转变为黄铁矿型结构。另外，还总结和比较了几种金红石型结构二氧化物的压致相变特点，得出第Ⅳ主族元素的金红石型结构氧化物有很好的规律性，发生的相变序列基本一致；并随着金属阳离子半径的增大，发生相变的压力值也相应地递减，各氧化物的体积模量值相应地减小。     

Chemical bonding in isolated molecules and crystals of zwitterionic pentacoordinate silicon chelates

The electronic structures of a number of zwitterionic pentacoordinate silicon chelates were investigated using the results of X-ray diffraction studies and quantum-chemical calculatoins by the MPW1PW91/6-311G(d) method. The topological analysis of the electron density distribution function and the study in the framework of the natural bond orbital partitioning scheme showed that the character of chemical bonding in the axial fragments of the molecules under consideration changes from dative to three-center, four-electron as the silicon atom assumes a trigonal-bipyramidal coordination.     

What Is Its Real Existing Form?——Theoretical and Experimental Studies on 2-Mercaptobenzothiazole

1 INTRODUCTION The study of heterocyclic molecules with aroma- tic rings and their absorptions on metals is of con- siderable importance from both theoretical and te- chnological points of view. These molecules are in- teresting because of their applications as corrosion inhibitors and flotation collectors, and their abilities to form self-assembly layers[1]. 2-Mercaptobenzo- thiazole (C7H5NS2, in the following MBT) is an important heterocyclic molecule, which can be used as corrosion …     

Quantum-Chemical Study of Structural and Energy Characteristics of Benzonitrile Dimers

Ab initio MP2 calculations with several basis sets proved the existence of a stable benzonitrile dimer with a planar structure and a short contact between the H atom of one molecule and the N atom of another. The structure is greatly stabilized by attraction between the neighboring oppositely directed dipoles and donor-acceptor interaction between the orbital of the lone electron pair of the N′ atom and the vacant antibonding orbital localized on the C-H bond.Original Russian Text Copyright © 2004 by O. V. Sizova, E. P. Sokolova, V. I. Baranovskii, D. A. Rozmanov, and O. A. Tomashenko__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 807–815, September–October, 2004.