Subcomponent Self-Assembly of a Cyclic Tetranuclear FeII Helicate in a Highly Diastereoselective Self-Sorting Manner

An enantiomerically pure diamine based on the 4,15-difunctionalized [2.2]paracyclophane scaffold and 2-formylpyridine self-assemble into an optically pure cyclic metallosupramolecular Fe₄L₆ helicate upon mixing with iron(II) ions in a diastereoselective subcomponent self-assembly process. The cyclic assembly results from steric strain that prevents the formation of a smaller linear dinuclear triple-stranded helicate, and hence, leads to the larger strain-free assembly that fulfils the maximum occupancy rule. Interestingly, use of the racemic diamine also leads to a racemic mixture of the homochiral cyclic helicates as the major product in a highly diastereoselective narcissistic chiral self-sorting manner given the fact that the assembly contains ten stereogenic elements, which can in principle give rise to 149 different diastereomers. The metallosupramolecular aggregates could be characterized by NMR, UV/Vis and CD spectroscopy, mass spectrometry, and X-ray crystallography.     

Observation of Photoelectron Circular Dichroism Using a Nanosecond Laser

Photoelectron circular dichroism (PECD) is a fascinating phenomenon both from a fundamental science aspect but also due to its emerging role as a highly sensitive analytic tool for chiral recognition in the gas phase. PECD has been studied with single-photon as well as multi-photon ionization. The latter has been investigated in the short pulse limit with femtosecond laser pulses, where ionization can be thought of as an instantaneous process. In this contribution, we demonstrate that multi-photon PECD still can be observed when using an ultra-violet nanosecond pulse to ionize chiral showcase fenchone molecules. Compared to femtosecond ionization, the magnitude of PECD is similar, but the lifetime of intermediate molecular states imprints itself in the photoelectron spectra. Being able to use an industrial nanosecond laser to investigate PECD furthermore reduces the technical requirements to apply PECD in analytical chemistry.     

External control of a metal-insulator transition in GaMnAs wires

Quantum transport in disordered ferromagnetic (III,Mn)V semiconductors is studied theoretically. Mesoscopic wires exhibit an Anderson disorder-induced metal-insulator transition that can be controlled by a weak external magnetic field. This metal-insulator transition should also occur in other materials with large anisotropic magnetoresistance effects. The transition can be useful for studies of zero-temperature quantum critical phase transitions and fundamental material properties.     

Experimental and numerical investigation of a stagnation pulverised coal flame

A multi-stream Flamelet Progress Variable (FPV) model, specifically developed for coal combustion, is proposed. The model accounts for the different fuel streams associated with the volatile and char burnout products. The applicability of the new FPV model is investigated in a laminar stagnation pulverized coal flame. The flame considered is a premixed mixture of CH₄, O₂ and N₂, carrying pulverized coal particles, stabilized in an impinging wall. Spontaneous emissions of OH*, CH* and C${}_2^{*}$ are measured to identify the flame. The 1D numerical simulations of the experimental conditions are able to reproduce the main features of the flame. The applicability of the multi-stream FPV model to coal combustion is further evaluated with the a posteriori analysis of the FPV results, comparing the results with a reference model, where the species are fully transported and the chemistry directly evaluated. Then, with the budget analysis, the influence of the control variables used to build the look-up table is assessed by examining the conditional contributions to the overall transport terms of scalar quantities (e.g. species, temperature). The results of both analyses show that the proposed multi-stream FPV model can accurately predict the main features of coal combustion, with only minor issues related to the manifold used to build the look-up table.     

Synthesis of μ2-Oxo-Bridged Iron(III) Tetraphenylporphyrin–Spacer–Nitroxide Dimers and their Structural and Dynamics Characterization by using EPR and MD Simulations

Iron(III) porphyrins have the propensity to form μ₂-oxo-dimers, the structures of which resemble two wheels on an axle. Whereas their crystal structure is known, their solution structure and internal dynamics is not. In the present work, the structure and dynamics of such dimers were studied by means of electron paramagnetic resonance (EPR) spectroscopy and quantum chemistry based molecular dynamics (MD) simulations by using the semiempirical tight-binding method (GFN-xTB). To enable EPR investigation of the dimers, a nitroxide was attached to each of the tetraphenylporphyrin cores through a linear and a bent linker. The inter-nitroxide distance distributions within the dimers were determined by continuous-wave (cw)-EPR and pulsed electron–electron double resonance (PELDOR or DEER) experiments and, with the help of MD, interpreted in terms of the rotation of the porphyrin planes with respect to each other around the Fe–O–Fe axis. It was found that such rotation is restricted to the four registers defined by the phenyl substituents. Within the registers, the rotation angle swings between 30° and 60° in the proximal and between 125° and 145° in the distal register. With EPR, all four angles were found to be equally populated, whereas the 30° and 145° angles are strongly favored to the expense of the 60° and 125° angles in the MD simulation. In either case, the internal dynamics of these dimers thus resemble the motion of a step motor.     

Controlled Radical Polymerization of Ethylene Using Organotellurium Compounds

The first successfully controlled radical polymerization (CRP) of ethylene is reported using several organotellurium chain‐transfer agents (CTAs) under mild conditions (70 °C, 200 bar of ethylene) within the concept of organotellurium‐mediated radical polymerization (TERP). In contrast to preceding works on CRPs of ethylene applying reversible addition–fragmentation chain‐transfer (RAFT), the TERP system provided a high livingness and chain‐end functionalization of polyethylene chains. Molar‐mass distributions with dispersities between 1.3 and 2.1 were obtained up to average molar masses of 5000 g mol^?1. As in the RAFT system, the high reactivity of the growing polyethylenyl radical led to an inherent side reaction. For the presented TERP systems, however, this side reaction did not result in dead chains, while it could even be effectively suppressed by a good choice of the CTA.