Dynamic Supramolecular Polymers Based on Benzene‐1,3,5‐tricarboxamides: The Influence of Amide Connectivity on Aggregate Stability and Amplification of Chirality

N‐Centred benzene‐1,3,5‐tricarboxamides (N‐BTAs) composed of chiral and achiral alkyl substituents were synthesised and their solid‐state behaviour and self‐assembly in dilute alkane solutions were investigated. A combination of differential scanning calorimetry (DSC), polarisation optical microscopy (POM) and X‐ray diffraction revealed that the chiral N‐BTA derivatives with branched 3,7‐dimethyloctanoyl chains were liquid crystalline and the mesophase was assigned as Col_ho. In contrast, N‐BTA derivatives with linear tetradecanoyl or octanoyl chains lacked a mesophase and were obtained as crystalline compounds. Variable‐temperature infrared spectroscopy showed the presence of threefold, intermolecular hydrogen bonding between neighbouring molecules in the mesophase of the chiral N‐BTAs. In the crystalline state at room temperature a more complicated packing between the molecules was observed. Ultraviolet and circular dichroism spectroscopy on dilute solutions of N‐BTAs revealed a cooperative self‐assembly behaviour of the N‐BTA molecules into supramolecular polymers with preferred helicity when chiral alkyl chains were present. Both the sergeants‐and‐soldiers as well as the majority‐rules principles were operative in stacks of N‐BTAs. In fact, the self‐assembly of N‐BTAs resembles closely that of their carbonyl (C?O)‐centred counterparts, with the exception that aggregation is weaker and amplification of chirality is less pronounced. The differences in the self‐assembly of N‐ and C?O‐BTAs were analysed by density functional theory (DFT) calculations. These reveal a substantially lower interaction energy between the monomeric units in the supramolecular polymers of N‐BTAs. The lower interaction energy is due to the higher energy penalty for rotation around the Ph? NH bond compared to the Ph? CO bond and the diminished magnitude of dipole–dipole interactions. Finally, we observed that mixed stacks are formed in dilute solution when mixing N‐BTAs and C?O BTAs.     

Magnetic nanostructures by adaptive twinning in strained epitaxial films

We exploit the intrinsic structural instability of the Fe(70)Pd(30) magnetic shape memory alloy to obtain functional epitaxial films exhibiting a self-organized nanostructure. We demonstrate that coherent epitaxial straining by 54% is possible. The combination of thin film experiments and large-scale first-principles calculations enables us to establish a lattice relaxation mechanism, which is not expected for stable materials. We identify a low twin boundary energy compared to a high elastic energy as key prerequisite for the adaptive nanotwinning. Our approach is versatile as it allows to control both, nanostructure and intrinsic properties for ferromagnetic, ferroelastic, and ferroelectric materials.     

About an analytical approach to a quasicontinuum method via Γ-convergence

We report on an analytical study of a quasicontinuum method in the context of fracture mechanics in a one-dimensional setting. To this end, we compare the asymptotic behaviour of a discrete model with nearest and next-to-nearest neighbour interactions of Lennard-Jones type and its quasicontinuum approximation via Γ-convergence. In case of fracture it turns out that one has to coarse grain in the continuum region and at the atomistic/continuum interface in order to capture the same behavior as the atomistic model, while this is not needed if the boundary conditions are such that the system behaves elastically. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Analysis and numerical simulation of magnetic forces between rigid polygonal bodies. Part I: Analysis

The mathematical and physical analysis of magnetoelastic phenomena is a topic of ongoing research. Different formulae have been proposed to describe the magnetic forces in macroscopic systems. We discuss several of these formulae in the context of rigid magnetized bodies. In case the bodies are in contact, we consider formulae both in the framework of macroscopic electrodynamics and via a multiscale approach, i.e., in a discrete setting of magnetic dipole moments. We give mathematically rigorous proofs for domains of polygonal shape (as well as for more general geometries) in two and three space dimensions. In an accompanying second article, we investigate the formulae in a number of numerical experiments, where we focus on the dependence of the magnetic force on the distance between the bodies and on the case when the two bodies are in contact. The aim of the analysis as well as of the numerical simulation is to contribute to the ongoing debate about which formula describes the magnetic force between macroscopic bodies best and to stimulate corresponding real-life experiments.