The Phosphorus Bond,or the Phosphorus-Centered Pnictogen Bond: The Covalently Bound Phosphorus Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor

The phosphorus bond in chemical systems, which is an inter- or intramolecular noncovalent interaction, occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a covalently or coordinately bonded phosphorus atom in a molecular entity and a nucleophile in another, or the same, molecular entity. It is the second member of the family of pnictogen bonds, formed by the second member of the pnictogen family of the periodic table. In this overview, we provide the reader with a snapshot of the nature, and possible occurrences, of phosphorus-centered pnictogen bonding in illustrative chemical crystal systems drawn from the ICSD (Inorganic Crystal Structure Database) and CSD (Cambridge Structural Database) databases, some of which date back to the latter part of the last century. The illustrative systems discussed are expected to assist as a guide to researchers in rationalizing phosphorus-centered pnictogen bonding in the rational design of molecular complexes, crystals, and materials and their subsequent characterization.     

基于斜向背散射偏振拉曼光谱的{100}c-Si面内应力分析

复杂应力状态下应力分量的解耦分析对半导体的设计和制造具有重要意义。本文开展了方法学研究,首先建立了{100}晶面族单晶硅面内应力分量解耦分析模型,基于该模型,通过改变入射光和散射光的几何构型和偏振构型,可得到单晶硅拉曼频移与应力分量的解析关系。在此基础上,提出了一种利用斜向背散射偏振拉曼光谱在不同倾角、偏振方向和样品旋转角度下开展原位拉曼探测实现应力分量解耦分析的实用技术。本文通过实验验证了该方法的可靠性和适用性。     

Synthesis, Crystal Structure and Electrochemical Properties of One-dimensional Chain Coordination Polymer [Co(Ⅱ)(C6H5CH=CHCOOH)2(4,4''-bipy)(H2O)5]n

A one-dimensional chain coordination polymer [Co(Ⅱ)(C6H5CH=CHCOOH)2(4,4'-bipy)(H2O)5]n has been synthesized with cinnamylic acid, 4,4'-bipy and cobaltous chloride as raw materials. Crystal data for this complex: monoclinic, space group P21/c, a - 1.1481(3), b =1.1230(2), c = 1.1759(3) nm, β = 97.054(4)°, V = 1.5046(6) nm3, Mr= 617.50, Dc = 1.363 g/cm3, Z= 2, μ(MoKα) = 0.627 mm-1, F(000) = 646, S = 1.062, R 0.0443 and wR = 0.1178. The crystal structure shows that two neighboring cobalt(Ⅱ) ions are linked together by one 4,4'-bipy, and the whole complex molecule adopts a one-dimensional chain structure. Each cobalt(Ⅱ) ion is coordinated with two nitrogen atoms from two 4,4'-bipy molecules and four oxygen atoms from four water molecules, giving a distorted octahedral coordination geometry. The electrochemical properties were analyzed by combining with the crystal structure.     

Das Pyren und der Einfluß von Substitution oder Komplexie-rung auf seine Geometrie und Packung im kristallinen Zustand

The crystal structures of pyrene and substituted and complexed derivatives of pyrene have been investigated by X-ray and neutron diffraction. The geometry of the pyrene skeleton has been determined experimentally with high accuracy and calculated by quantum chemical methods. In the cases reported in the literature and cited here the pyrene skeleton has the molecular symmetry mmm or mm2 with values for the bond lengths of the six symmetrically independent bondsa, b, c, d, e, f differing significantly in the limits of error. Mean values of a number of experimental and theoretical bond lengths are given and can be considered as standard values for the mm2 symmetric pyrene skeleton. In the case of substitution of the pyrene in 3-position with a polar heterocyclic molecule of the azomethine-imine type the mm2 symmetry vanishes, a C–H ... N intramolecular hydrogen bond arises and the directly neighbouring pyrene units are not packed parallel with their planes to each other, but they are considerably tilted. Relatively narrow intermolekular C-C contacts, 3.314 and 3.368 Å, have been observed. The conclusion is drawn that the asymmetry of the pyrene molecule and a tilt of directly neighbouring pyrene units in the crystal packing can be induced by substitution e. g. with suitable polar heterocycles.

Juli 1985.     

在不加对称性限制的条件下采用不同的半经验方法研究酞菁的电荷分布和几何构型

在不加对称性限制的条件下采用不同的半经验方法CNDO,INDO,MINDO/3,MNDO和Pm3对自由酞菁(H₂Pc)进行几何构型最优化和电荷密度布居分析，并将所得结果与Am1方法以及X射线衍射和中子衍射数据的数据进行比较。结果表明只有从INDO方法得到的是桥式构型，而从CNDO,MINDO/3,MNDO,Am1,Pm3方法得到的都是键式构型。除INDO之外所有的这几种方法都对先前报道的几何构型扭曲给出进一步的支持证据。新近建立的半经验方法如MNDO,Am1,Pm3等看起来更适合于用     

Spectroscopic Studies of a Three-dimensional, Five-coordinated Copper(Ⅱ) Complex via Hydrogen Bonds: [Cu(PDA)(H_2O)_2](H_2PDA=Pyridine-2,6-dicarboxylic Acid)

IntroductionFive- coordinated complexes with d9- configuredcations have received much attention stereochemi-cally,spectrochemically and biologically,and havebeen comprehensively discussed[1] . Usually thereare two stable configurations for the copper( )complexes with five equal coordinating atoms:anapically elongated square pyramid( SP) and a com-pressed trigonal bipyramid( TBP) ,with an obviousenergetic preference for the latter coordination.When the ligands are rigid and provide angular d…     

Bis(2-(1H-imidazol-2-yl)-pyridine)copper(II): Effects of counteranions on the molecular and supramolecular structures

The synthesis and physical properties of bis(2-(1H-imidazol-2-yl)-pyridine)copper(II) with chloride, nitrate and perchlorate as counteranions have been described. Microanalysis, magnetic susceptibility, conductivity and various spectroscopic measurements have been used for the characterization of the complexes. The crystal structures of all three complexes have been determined. Intermolecular hydrogen-bonding interactions and the resulting self-assembly patterns for each of the species have been scrutinized. The chloride containing complex crystallizes as a trihydrate, where the metal ion is in a tetragonally elongated cis-N₄Cl₂ coordination sphere. This complex provides a three-dimensional honeycomb-like structure through N–H?Cl, O–H?Cl and O–H?O hydrogen bonds. In the nitrate containing species, one of the two counteranions coordinates to the metal centre to provide an irregular N₄O₂ coordination sphere, while the other counteranion, with the help of a lattice water molecule, assembles a ladder-like structure via N–H?O and bifurcated O–H?O,O hydrogen bonds. A one-dimensional polymeric species has been formed when perchlorate is the counteranion. Here one of the two perchlorates acts as a bridge between the metal centres that are in tetragonally elongated trans-N₄O₂ coordination spheres. This polymeric chain, together with the second perchlorate and a water molecule, form a ribbon-like structure due to N–H?O and O–H?O hydrogen bonds.     

Generalized Einstein manifolds

A Finslerian manifold is called a generalized Einstein manifold (GEM) if the Ricci directional curvature R(u,u) is independent of the direction. Let F⁰(M, g_t) be a deformation of a compact n-dimensional Finslerian manifold preserving the volume of the unitary fibre bundle W(M). We prove that the critical points g₀ F⁰(g_t) of the integral I(g_t) on W(M) of the Finslerian scalar curvature (and certain functions of the scalar curvature) define a GEM. We give an estimate of the eigenvalues of Laplacian Δ defined on W(M) operating on the functions coming from the base when (M, g) is of minima fibration with a constant scalar curvature H admitting a conformal infinitesimal deformation (CID). We obtain λ ≥ H/(n − 1) (Δf = λf). If M is simply connected and λ = H/(n − 1), then (M, g) is Riemannian and is isometric to an n-sphere. We first calculate, in the general case, the formula of the second variationals of the integral I (g_t) for G = g₀, then for a CID we show that for certain Finslerian manifolds, I″(g₀) > 0. Applications to the gravitation and electromagnetism in general relativity are given. We prove that the spaces characterizing Einstein-Maxwell equations are GEMs.     

非线性水波Hamilton系统理论与应用研究进展

概述了辛几何理论与辛算法在Hamilton力学中的应用，综述非线性水波的Hamilton理论研究进展．阐述非线性水波Hamilton变分原理与方法的优越性与局限性，探讨KdV方程和BBM方程的Hamilton描述、对称性与守恒律，提出非线性水波Hamilton描述研究中有待进一步研究的问题和解法设想．     

考虑剪切效应层合板的Hamilton体系及辛几何方法

基于ＹＮＳ层合板理论,通过对混合能变分原理的修正,建立了层合板问题的Ｈａｍｉｌｔｏｎ正则方程。在辛几何数学框架下,采用共轭辛正交归一关系给出精确解。并与经典层板理论进行了比较。