Enantioselective photochemical synthesis of a simple alkene via the solid state ionic chiral auxiliary approach

Irradiation of cis-bicyclo[4.3.0]non-8-ylacetophenone derivatives (1) in solution and the solid state yields cis-3a,4,5,6,7,7a-hexahydro-1H-indene (2) via a Norrish type II cleavage process. Asymmetric induction studies were conducted by providing the reactants with carboxylic acid substituents to which ionic chiral auxiliaries were attached through salt formation with optically pure amines. Irradiation of the salts (5 in total) in the crystalline state gave enantiomeric excesses of up to 44%. Single-crystal X-ray diffraction studies were performed on ketone 1a as well as salts 1d and 1g, and on this basis, the structure-reactivity relationships involved are discussed.     

Possibilities of powder X-ray diffraction methods in determining structural characteristics of carbon materials

The possibilities of using powder X-ray diffraction methods in the study of carbon materials are discussed. To determine the phase composition of the crystalline materials the X-ray phase analysis is employed; the real structure is established by the harmonic analysis of diffraction profiles; the structural features and phase composition of the nanomaterials are found by the radial electron density distribution function.     

Structural understanding of a molecular material that is accessed only by a solid-state desolvation process: the scope of modern powder X-ray diffraction techniques

Many molecular materials cannot be prepared as a "pure" (nonsolvate) crystalline phase by conventional crystal growth from solution due to the facile formation of solvate structures. In such cases, it may be possible to obtain the pure phase by a solid-state desolvation process, although such processes are generally associated with loss of crystal integrity, yielding a microcrystalline powder of the pure phase. This paper demonstrates the utility of modern powder X-ray diffraction techniques for obtaining structural understanding in such cases, focusing on a particular member of a structural family that is of wider relevance within the context of crystal engineering and design.     

Ammonia Oxide as a Building Block for High-Performance and Insensitive Energetic Materials

3,5-Dinitrimino-1,2,4-triazole ( 2 ) with three protons has the potential of deprotonation to form energetic salts. Neutralization of 2 with 50 % hydroxylamine in varying molar ratios leads to the formation of the corresponding mono/dihydroxylammonium energetic salts. Additionally compound 5 , an ammonia oxide adduct of dihydroxylammonium 3,5-dinitramino-1,2,4-triazolate, was prepared when excess hydroxylamine was used. The structures of 3 – 5 are supported by single-crystal X-ray diffraction. The energetic properties of the new materials are competitive. Utilization of ammonia oxide adducts in hydroxylammonium energetic salts could lead to future practical applications as energetic materials.     

Contemporary Advances in the Use of Powder X-Ray Diffraction for Structure Determination

Many crystalline solids cannot be prepared in the form of single crystals of sufficient size and/or quality for investigation using single-crystal X-ray diffraction techniques, and the opportunity to carry out structure determination using powder diffraction data is therefore essential to understand the structural properties of such materials. Although the refinement stage of the structure determination process can be carried out fairly routinely from powder diffraction data using the Rietveld profile refinement technique, solving crystal structures directly from powder data is associated with several intrinsic difficulties. Nevertheless, substantial progress has been made in recent years in the scope and potential of techniques in this field. This article aims to highlight the types of structural problems for which structure determination may now be tackled directly from powder diffraction data, and contemporary applications across several chemical disciplines are presented. A brief survey of the underlying methodologies is given, with some emphasis on recently developed techniques for carrying out the structure-solution stage of the structure-determination process.     

New Approaches for Solving Crystal Structures from Powder Diffraction Data

The determination of crystal structures from single crystal diffraction data can generally be carried out routinely and straightforwardly. However, many crystalline solids can be obtained only as microcrystalline powders and are not suitable for investigation by conventional single crystal diffraction methods. In the past, this problem has limited the ability to elucidate the structural properties of such materials. For the wide range of materials in this category, there is clearly a pressing need to develop and exploit techniques that allow crystal structures to be solved from powder diffraction data. Although traditional techniques for structure solution from powder diffraction data have been applied successfully in several cases, these techniques have certain intrinsic limitations, and for the case of organic molecular crystals the challenges that must be overcome are particularly severe. For these reasons, our recent research has focused on the development and implementation of new methodologies for structure solution from powder diffraction data, leading to new “direct-space” techniques for structure solution in which a hypersurface based on the profile R-factor is searched using Monte Carlo or Genetic Algorithm techniques. This paper presents a brief overview of the problems and challenges associated with structure solution from powder diffraction data. The foundations of the techniques that we have developed are described, and illustrative examples (from the field of organic molecular crystals) are given to highlight the application of these techniques.     

Hybrid composites of monodisperse pi-conjugated rodlike organic compounds and semiconductor quantum particles

Composite materials of quantum particles (Q-particles) arranged in layers within crystalline powders of pi-conjugated, rodlike dicarboxylic acids are reported. The synthesis of the composites, either as three-dimensional crystals or as thin films at the air-water interface, comprises a two-step process: 1) The preparation of the Cd salts 6 (Cd), 8 (Cd) or Pb salts 6 (Pb), 8 (Pb) of the oligo(p-phenyleneethynylene)dicarboxylic acids 6 (H), 8 (H), in which the metal ions are arranged in ribbons and are separated by the long axis of the organic molecules, as demonstrated by X-ray powder diffraction analysis of the solids and grazing incidence X-ray diffraction analysis of the films on water. 2) Topotactic solid/gas reaction of these salts with H(2)S to convert the metal ions into Q-particles of CdS or PbS embedded in the organic matrix that consists of the acids 6 (H) and 8 (H). These hybrid materials have been characterized by X-ray photoelectron spectroscopy and transmission electron microscopy.     

Effect of enantiomeric excess on thermotropic and electro-optical properties of ferroelectric sulphinate liquid crystals

The liquid crystalline behaviour and the electro-optical properties of mixtures of two pure ferroelectric enantiomers are studied as a function of the enantiomeric excess and compared with those of the corresponding racemate. It appears clearly that, depending upon the value of the enantiomeric excess, distinct thermotropic sequences are observed. The transition temperatures change significantly, and an additional SmB phase is observed for the racemate and for the mixtures of neighbouring concentrations. Moreover, the variation of the spontaneous polarization as a function of the enantiomeric excess is found to be strongly nonlinear. All these experimental observations show unambiguously that the thermotropic behaviour, the polar order, and consequently all the related electro-optical properties of the ferroelectric liquid crystal materials studied in the present work depend significantly upon the optical purity of the materials.     

How to determine structures when single crystals cannot be grown: opportunities for structure determination of molecular materials using powder diffraction data

Many crystalline solids cannot be prepared as single crystals of sufficient size and/or quality for structure determination to be carried out using single crystal X-ray diffraction techniques. In such cases, when only polycrystalline powders of a material are available, it is necessary instead to tackle structure determination using powder X-ray diffraction. This article highlights recent developments in the opportunities for determining crystal structures directly from powder diffraction data, focusing on the case of molecular solids and giving particular attention to the most challenging stage of the structure determination process, namely the structure solution stage. In particular, the direct-space strategy for structure solution is highlighted, as this approach has opened up new opportunities for the structure determination of molecular solids. The article gives an overview of the current state-of-the-art in structure determination of molecular solids from powder diffraction data. Relevant fundamental aspects of the techniques in this field are described, and examples are given to highlight the application of these techniques to determine crystal structures of molecular materials.     

On the spontaneous induction of chirality in the preparation of Werner's complex cis-[CoBr(NH3)(en)2]Br2

The product obtained directly from the standard reaction to produce Werner's complex cis-[CoBr(NH3)(en)2]Br2 is shown, via structure determination from powder X-ray diffraction data, to be a racemic crystalline phase; implications of this observation in relation to previous reports that this reaction leads to significant enantiomeric excesses are discussed.     

Three-dimensional electron diffraction for porous crystalline materials: structural determination and beyond

Porous crystalline materials such as zeolites, metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) have attracted great interest due to their well-defined pore structures in molecular dimensions. Knowing the atomic structures of porous materials is crucial for understanding their properties and exploring their applications. Many porous materials are synthesized as polycrystalline powders, which are too small for structure determination by X-ray diffraction. Three-dimensional electron diffraction (3DED) has been developed for studying such materials. In this Minireview, we summarize the recent developments of 3DED methods and demonstrate how 3DED revolutionized structural analysis of zeolites, MOFs, and COFs. Zeolites and MOFs whose structures remained unknown for decades could be solved. New approaches for design and targeted synthesis of novel zeolites could be developed. Moreover, we discuss the advances of structural analysis by 3DED in revealing the unique structural features and properties, such as heteroatom distributions, mixed-metal frameworks, structural flexibility, guest–host interactions, and structure transformation.

Three-dimensional electron diffraction is a powerful tool for accurate structure determination of zeolite, MOF, and COF crystals that are too small for X-ray diffraction. By revealing the structural details, the properties of the materials can be understood, and new materials and applications can be designed.     

Supramolecular Assembly and Chirality of Synthetic Carbohydrate Materials

Hierarchical carbohydrate architectures serve multiple roles in nature. Hardly any correlations between the carbohydrate chemical structures and the material properties are available due to the lack of standards and suitable analytic techniques. Therefore, designer carbohydrate materials remain highly unexplored, as compared to peptides and nucleic acids. A synthetic D -glucose disaccharide, DD , was chosen as a model to explore carbohydrate materials. Microcrystal electron diffraction (MicroED), optimized for oligosaccharides, revealed that DD assembled into highly crystalline left-handed helical fibers. The supramolecular architecture was correlated to the local crystal organization, allowing for the design of the enantiomeric right-handed fibers, based on the L -glucose disaccharide, LL , or flat lamellae, based on the racemic mixture. Tunable morphologies and mechanical properties suggest the potential of carbohydrate materials for nanotechnology applications.     

Effect of magnesium doping on the properties and crystalline perfection of bis(thiourea)zinc(II) chloride crystals

In this article, the effect of magnesium doping on the properties of bis(thiourea)zinc(II) chloride (BTZC) crystals has been described. The incorporation of Mg(II) into the crystal lattice was confirmed by energy dispersive X-ray spectroscopy and quantified by inductively coupled plasma technique. The powder X-ray diffraction and FT-IR spectral analyses indicate that the crystal undergoes considerable stress as result of doping. SEM studies of pure and doped samples indicate the formation of structural defect centers in BTZC crystals. The TG?CDTA studies reveal the purity of the materials, and no decomposition is observed up to the melting point. Improved crystalline perfection by doping is observed by high-resolution X-ray diffraction. High transmittance is observed, and the cutoff ?? is ~295?nm.     

Carbonic acid: from polyamorphism to polymorphism

Layers of glassy methanolic (aqueous) solutions of KHCO3 and HCl were deposited sequentially at 78 K on a CsI window, and their reaction on heating in vacuo in steps from 78 to 230 K was followed by Fourier transform infrared (FTIR) spectroscopy. After removal of solvent and excess HCl, IR spectra revealed formation of two distinct states of amorphous carbonic acid (H2CO3), depending on whether KHCO3 and HCl had been dissolved in methanol or in water, and of their phase transition to either crystalline alpha- or beta-H2CO3. The main spectral features in the IR spectra of alpha- and beta-H2CO3 are observable already in those of the two amorphous H2CO3 forms. This indicates that H-bond connectivity or conformational state in the two crystalline phases is on the whole already developed in the two amorphous forms. The amorphous nature of the precursors to the two crystalline polymorphs is confirmed using powder X-ray diffraction. These diffractograms also show that alpha- and beta-amorphous H2CO3 are two distinct structural states. The variety of structural motifs found within a few kJ/mol in a computational search for possible crystal structures provides a plausible rationalization for (a) the observation of more than one amorphous form and (b) the retention of the motif observed in the amorphous form in the corresponding crystalline form. The polyamorphism inferred for carbonic acid from our FTIR spectroscopic and powder X-ray diffraction studies is special since two different crystalline states are linked to two distinct amorphous states. We surmise that the two amorphous states of H2CO3 are connected by a first-order-like phase transition.     

Solid-state structural properties of 2,4,6-trimethoxybenzene derivatives, determined directly from powder X-ray diffraction data in conjunction with other techniques

Structural properties of 2,4,6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzyl alcohol and 2,4,6-trimethoxyacetophenone have been determined directly from powder X-ray diffraction data, using the direct-space Genetic Algorithm (GA) technique for structure solution followed by Rietveld refinement. Structural similarities and contrasts within this family of materials are elucidated. The work illustrates the value of utilizing information from other sources, including spectroscopic data and computational techniques, as a means of augmenting the structural knowledge established from the powder X-ray diffraction data.     

Synthesis of CuInSe<Subscript>2</Subscript> and CuGaSe<Subscript>2</Subscript> hexagonal microplates in oleic acid and oleylamine mixture

The compounds of I-II-VI₂ family are the leading materials in the second-generation thin film solar cells. In this paper, we reported the synthesis of CuGaSe₂ and CuInSe₂ hexagonal microplates in the mixture of oleylamine and oleic acid. Regular copper, indium, and gallium salts as well as selenium powder were used as the precursors with stoichiometric ratio. X-ray diffraction patterns and selected area electron diffraction characterization confirmed their high crystalline quality. Furthermore, control experiments indicated two possible mechanisms of morphology transformation. The synthetic method is simple and reproducible and the as-prepared nanomaterials might find their application in solar cells. The article is published in the original.     

Li1-xMxFePO4阴极材料的合成和电化学性能

应用聚丙烯酸盐热解法合成掺杂Cr3+或Mg2+、Mn2+、Ni2+的LiFePO4正极材料,研究掺杂离子对目标化合物电化学性质的影响.XRD和SEM实验表明,该材料微米级颗粒是由约200nm的粒子团聚而成的,具有橄榄石型结构,且未出现杂质相.电化学测试表明,掺Cr3+的LiFePO4在高倍率(3C)放电下的首周放电容量为97mAh/g,相当于0.15C率容量的66%,其循环性能优异,充分显示离子掺杂能显著改善材料的高倍率放电性能和循环性能.     

Lamellar bridged silsesquioxanes: self-assembly through a combination of hydrogen bonding and hydrophobic interactions

The synthesis of four bis(trialkoxysilylated) organic molecules capable of self-assembly--(EtO)3Si(CH2)3NHCONH-(CH2)n-NHCONH(CH2)3Si(OEt)3 (n = 9-12)--associating urea functional groups and alkylidene chains of variable length is described. These compounds behave as organogelators, forming supramolecular assemblies thanks to the intermolecular hydrogen bonding of urea groups. Whereas fluoride ion-catalysed hydrolysis in ethanol in the presence of a stoichiometric amount of water produced amorphous hybrids, acid-catalysed hydrolysis in an excess of water gave rise to the formation of crystalline lamellar hybrid materials through a self-organisation process. The structural features of these nanostructured organic/inorganic hybrids were analysed by several techniques: attenuated Fourier transformed infrared (ATR-FTIR), solid-state NMR spectroscopy (13C and 29Si), scanning and transmission electron microscopy (SEM and TEM) and powder X-ray diffraction (PXRD). The reaction conditions, the hydrophobic properties of the long alkylidene chains and the hydrogen-bonding properties of the urea groups are determining factors in the formation of these self-assembled nanostructured hybrid silicas.     

Two-Dimensional Crystallography of Amphiphilic Molecules at the Air–Water Interface

The advent of well-collimated, high-intensity synchrotron X-ray sources and the consequent development of surface-specific X-ray diffraction and fluorescence techniques have recently revolutionized the study of Langmuir monolayers at the air–liquid interface. These methods allowed for the first time the determination of the in-plane and vertical structure of such monolayers with a resolution approaching the atomic level. We briefly describe these methods, including grazing incidence X-ray diffraction, specular reflectivity, Bragg rods, standing waves, and surface fluorescence techniques, and review recent results obtained from them for Langmuir films. The methods have been successfully applied in the elucidation of the structure of crystalline aggregates of amphiphilic molecules such as alcohols, carboxylic acids and their salts, α-amino acids, and phospholipids at the water surface. In addition, it became possible to monitor by diffraction the growth and dissolution of the crystalline self-aggregates as well as structural changes occurring by phase transitions. Furthermore, the surface X-ray methods shed new light on the structure of the underlying ionic layer of attached solvent or solute species. Examples are given where singly or doubly charged ions bound to the two-dimensional (2D) crystal form either an ordered or diffuse counterionic layer. Finally, the surface diffraction methods provide data on transfer of structural information from 2D clusters to 3D single crystals, which had been successfully accomplished by epitaxial-like crystallization both in organic and inorganic crystals.