Morphology and molecular organisation of liquid-crystalline perylene-3,4,9,10-tetra-(n-hexylester) deposited on a solid substrate

Liquid-crystalline perylene-3,4,9,10-tetra-(n-hexylester) forms characteristic dendritic or flower-like structures at room temperature when it is deposited on a hydrophilic glass substrate using the zone-casting technique. It was found that such unique structures were not possible to be created simply by recrystallisation of this dye from a liquid-crystalline columnar phase. On the basis of the observations using a confocal microscope and the study of wide angle X-ray scattering (WAXS) as well as the analysis of the absorption and fluorescence spectra, some conclusions, concerning the molecular organisation in the dendritic structure, are drawn. Based on the research, one can assume that the dendrites are formed by columnar molecular aggregates with the column axes parallel to the substrate. Such an organisation of the molecules can be interesting from the point of view of organic electronics.     

Size does matter! Label-free detection of small molecule–protein interaction

This review is focused on methods for detecting small molecules and, in particular, the characterisation of their interaction with natural proteins (e.g. receptors, ion channels). Because there are intrinsic advantages to using label-free methods over labelled methods (e.g. fluorescence, radioactivity), this review only covers label-free techniques. We briefly discuss available techniques and their advantages and disadvantages, especially as related to investigating the interaction between small molecules and proteins. The reviewed techniques include well-known and widely used standard analytical methods (e.g. HPLC-MS, NMR, calorimetry, and X-ray diffraction), newer and more specialised analytical methods (e.g. biosensors), biological systems (e.g. cell lines and animal models), and in-silico approaches.     

Multigrid preconditioning for time-periodic Navier–Stokes problems

We propose to solve time-periodic Navier–Stokes problems by a discrete Fourier transform in time. Truncating the Fourier series yields a nonlinear system of equations for the unknown Fourier coefficients. Its solution by Picard iteration requires to solve a sequence of linear systems of equations. The focus of this work is on an efficient method to solve these linear systems. We employ GMRES, complemented by an optimal block triangular preconditioner. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Germaborenes: Borylene Transfer Agents for the Synthesis of Iminoboranes

Halide and phenyl substituted germaborenes were shown to react with azides at room temperature and transfer a borylene moiety to give iminoboranes. This iminoborane synthesis based on a borylene transfer route was investigated computationally in the case of the phenyl substituted germaborene.     

Phosphine-Stabilized Pnictinidenes

The reaction of the intramolecular germylene-phosphine Lewis pair (o-PPh₂)C₆H₄GeAr* ( 1 ) with Group 15 element trichlorides ECl₃ (E=P, As, Sb) was investigated. After oxidative addition, the resulting compounds (o-PPh₂)C₆H₄(Ar*)Ge(Cl)ECl₂ ( 2 : E=P, 3 : E=As, 4 : E=Sb) were reduced by using sodium metal or LiHBEt₃. The molecular structures of the phosphine-stabilized phosphinidene (o-PPh₂)C₆H₄(Ar*)Ge(Cl)P ( 5 ), arsinidene (o-PPh₂)C₆H₄(Ar*)Ge(Cl)As ( 6 ) and stibinidene (o-PPh₂)C₆H₄(Ar*)Ge(Cl)Sb ( 7 ) are presented; they feature a two-coordinate low-valent Group 15 element. After chloride abstraction, a cyclic germaphosphene [(o-PPh₂)C₆H₄(Ar*)GeP] [B(C₆H₃(CF₃)₂)₄] ( 8 ) was isolated. The ³¹P NMR data of the germaphosphene were compared with literature examples and analyzed by quantum chemical calculations. The phosphinidene was treated with [iBu₂AlH]₂, and the product of an Al−H addition to the low-valent phosphorus atom (o-PPh₂)C₆H₄(Ar*)Ge(H)P(H)Al(C₄H₉)₂ ( 9 ) was characterized.     

Rb[Li5Si2O7] – A Latecomer in the Family of Alkali Lithosilicates Hiding a Green-Emitting Lithosilicate

In order to expand the field of alkali lithosilicates, a new representative of the substance class with a previously unknown structure type was found based on solid-state synthesis. The novel compound with the sum formula Rb[Li₅Si₂O₇] crystallizes in the orthorhombic space group Pbcm (no. 57) with a=7.6269(3), b=9.5415(4), and c=9.4095(3) Å by means of single-crystal X-ray diffraction. The structure consists of a highly condensed lithosilicate framework, built up of corner- and edge-linked [LiO₄]-tetrahedra and [Si₂O₇]-units, and the rubidium ions aligned in channels. Suitable crystals of the material were obtained using sealed tantalum ampoules as reaction tube at a temperature of 750 °C. The new compound was further characterized via powder diffraction, Rietveld analysis, and EDX measurements. At first glance, Eu²⁺-doped Rb[Li₅Si₂O₇] reveals an intense green luminescence. In-depth crystal analysis shows that a core-shell formation is present even for apparently high quality single-crystals. As a minority phase, the known green phosphor RbLi[Li₃SiO₄]₂:Eu²⁺ is the origin of the luminescence, representing a tiny core inside of the particles surrounded by a large matrix of transparent Rb[Li₅Si₂O₇] dominating the single-crystal diffraction pattern.     

Pentacoordinate Phosphorus in a High‐Pressure Polymorph of Phosphorus Nitride Imide P4N6(NH)

Coordination numbers higher than usual are often associated with superior mechanical properties. In this contribution we report on the synthesis of the high‐pressure polymorph of highly condensed phosphorus nitride imide P₄N₆(NH) representing a new framework topology. This is the first example of phosphorus in trigonal‐bipyramidal coordination being observed in an inorganic network structure. We were able to obtain single crystals and bulk samples of the compound employing the multi‐anvil technique. γ‐P₄N₆(NH) has been thoroughly characterized using X‐ray diffraction, solid‐state NMR and FTIR spectroscopy. The synthesis of γ‐P₄N₆(NH) gives new insights into the coordination chemistry of phosphorus at high pressures. The synthesis of further high‐pressure phases with higher coordination numbers exhibiting intriguing physical properties seems within reach.     

An Air‐Stable Heterobimetallic Si2M2 Tetrahedral Cluster

Air‐ and moisture‐stable heterobimetallic tetrahedral clusters [Cp(CO)₂MSiR]₂ (M=Mo or W; R=SitBu₃) were isolated from the reaction of N‐heterocyclic carbene (NHC) stabilized silyl(silylidene) metal complexes Cp(CO)₂M=Si(SitBu₃)NHC with a mild Lewis acid (BPh₃). Alternatively, treatment of the NHC‐stabilized silylidene complex Cp(CO)₂W=Si(SitBu₃)NHC with stronger Lewis acids such as AlCl₃ or B(C₆F₅)₃ resulted in the reversible coordination of the Lewis acid to one of the carbonyl ligands. Computational investigations revealed that the dimerization of the intermediate metal silylidyne (M≡Si) complex to a tetrahedral cluster instead of a planar four‐membered ring is due to steric bulk.