Supramolecular architectures with ladder and lamellar topologies using metal-ligand coordination units via C–H···Cl and O–H···Cl hydrogen bonding

New Mn^II/Cu^II/Zn^II complexes [(L¹)MnCl₂] (1), [(L²)CuCl₂]·0.5H₂O (2) and [(L²)ZnCl(H₂O)][ClO₄] (3), containing (2-pyridyl)alkylamine ligands, N-methyl-N,N-bis(2-pyridylmethyl)amine (L¹) and methyl[2-(2-pyridyl)ethyl](2-pyridylmethyl)amine (L²), have been prepared and characterized, including X-ray crystallography. The most striking feature of the structures of these complexes is the formation of molecular ladder and lamellar topology through the crystal packing arrangement, determined by both strong O–H···Cl and weak (however, multiple) C–H···Cl hydrogen-bonding interactions, to maintain the neutral/cationic metal-ligand coordination units linked to each other. In 3, additional secondary interactions are observed involving coordinated solvent and the counter-ion. The results presented here demonstrate that (i) the choice of organic ligands to provide flexibility and inherent potential to participate in hydrogen-bonding interactions, (ii) the coordination geometry preferences of metal ions, (iii) the number of metal-bound chloride ion and (iv) the presence of solvent/counter-anion have a great influence on supramolecular network topology.     

APICOPHILICITY AND RING-STRAIN IN FIVE-COORDINATE PHOSPHORANES

Abstract

In order to dicuss mechanism in organophosphorus chemistry a number of assumptions have to be made. Among them are: (a) that substitutions at tetrahedral phosphorus proceed via five-coordinate intermediates; (b) these intermediates are trigonal bipyramidal; (c) they are formed by apical attack and decompose by apical loss; and (d) if sufficiently long-lived, they may undergo permutational isomerization, that is the ligands may alter their relative dispositions round the phosphorus, before going on to products or back to reactants.

Assuming that the course of a given substitution is dictated primarily by thermodynamic considerations, in order to understand the course of that substitution one needs to know how to assess the relative stabilities of the four isomeric tbps (trigonal bipyramids) that can be formed initially and of the others that could be formed by subsequent isomerization, the barriers to those isomerizations, and the relative rates of the various product-forming steps. We have concentrated on the first of these factors and this lecture describes our attempts to provide the necessary data.

The energy difference between two isomeric tbps can be analyzed in terms of changes in the relative apicophilicities¹ of the groups occupying apical positions, changes in ring-strain as small rings move between apical-equatorial and diequatorial positions, and changes in steric strain. I shall consider each of these in turn. Ligand subset symmetry may also have to be taken into account.^1,2     

A ladder conjugated polymer transducer for solid-contact Cu2+-selective electrodes

In recent years, there has been a pronounced interest in solid-contact ion-selective electrodes （SC-ISEs）, with emphasis on the use of conducting polymers as ion-to-electron transducer. In this work, a ladder conjugated polymer, thieno[3,2-b]thiophene （LCPT）, was investigated in fabricating Cu2＋-selective electrodes for the first time. The resulting electrodes were characterized by electrochemical impedance spectroscopy （EIS）, chronopotentiometry, and the water layer test. Results proved that the active LCPT facilitates the ion-to-electron transduction, and avoids the detrimental aqueous layer formed at the interface of SC-ISEs.     

H-Bonding Self-assembled Template-directed Synthesis of a Reactive Amide-bridged Ladder Polyvinylsiloxane

Ladder polysiloxanes (LPS) including both oxygen-bridged ladder polysilsesquioxanes (LPSQ) and organo-bridged ladder polysiloxanes (OLPS) are very important materials because of their excellent properties1. Adrianov et al. in 1960 attempted to prepare 1, …     

Preparation and Characterization of Ordered Ladder Like Polyphenylsilsesquioxane via Two-step Sol-gel Method

Soluble and ordered ladder like polyphenylsilsesquioxane was synthesized by a two-step sol-gel method including hydrolysis and polycondensation. The procedure was monitored by Fourier transform infrared spectroscopy and the presence of the ladder like structure was confirmed by X-ray techniques. 29Si NMR analysis shows a very narrow half peak width(δ<4) at δ -78.866 of the main chain unit C6H5SiO3/2 of polyphenylsilsesquioxane, indicating that the polyphenylsilsesquioxane has ordered ladder like structures ...     

RBNS的线性预测模型

传统的准备金方法都是基于聚合数据的,聚合数据是个体数据的汇总,它们丢失了许多有用信息,影响了准备金预测的准确性.本文提出了一个基于个体数据的线性预测模型,该模型不需要对数据的矩的具体形式进行假设,更不需要对数据的分布进行假设,而只需假设个体索赔数据的前两阶矩存在,具有适用范围广,简单易操作等特点.在文章的最后,通过随机模拟把提出的方法与著名的链梯法进行了对比,模拟结果显示,本文提出的方法是行之有效的.     

声表面波梯形谐振滤波器级联结构的研究

本对声表面波梯形谐振滤波器4级级联的5种不同级联结构进行了理论分析，计算出了其频响特性曲线。对5种不同结构的特性进行了比较，得出了不同结构在带宽、矩形系数、带外抑制等方面的特性，以期对以后实际器件的设计提供理论根据。     

功能彩色高分子合成技术进展

本文通过实例对功能彩色高分子的合成方法以及每种合成方法的原理、特点、发展历史和可实行性作了较详细的综述。     

Structural properties of Gerber-Shiu functions in dependent Sparre Andersen models

The structure of various Gerber-Shiu functions in Sparre Andersen models allowing for possible dependence between claim sizes and interclaim times is examined. The penalty function is assumed to depend on some or all of the surplus immediately prior to ruin, the deficit at ruin, the minimum surplus before ruin, and the surplus immediately after the second last claim before ruin. Defective joint and marginal distributions involving these quantities are derived. Many of the properties in the Sparre Andersen model without dependence are seen to hold in the present model as well. A discussion of Lundberg’s fundamental equation and the generalized adjustment coefficient is given, and the connection to a defective renewal equation is considered. The usual Sparre Andersen model without dependence is also discussed, and in particular the case with exponential claim sizes is considered.     

Spinful fermionic ladders at incommensurate filling: Phase diagram,local perturbations,and ionic potentials

We study the effect of external potential on transport properties of the fermionic two-leg ladder model. The response of the system to a local perturbation is strongly dependent on the ground state properties of the system and especially on the dominant correlations. We categorize all phases and transitions in the model (for incommensurate filling) and introduce “hopping-driven transitions” that the system undergoes as the inter-chain hopping is increased from zero. We also describe the response of the system to an ionic potential. The physics of this effect is similar to that of the single impurity, except that the ionic potential can affect the bulk properties of the system and in particular induce true long range order.