Reliable Computational Prediction of the Supramolecular Ordering of Complex Molecules under Electrochemical Conditions.

We propose a computationally lean, two-stage approach that reliably predicts self-assembly behavior of complex charged molecules on metallic surfaces under electrochemical conditions. Stage one uses ab initio simulations to provide reference data for the energies (evaluated for archetypical configurations) to fit the parameters of a conceptually much simpler and computationally less expensive force field of the molecules: classical, spherical particles, representing the respective atomic entities; a flat and perfectly conducting wall represents the metallic surface. Stage two feeds the energies that emerge from this force field into highly efficient and reliable optimization techniques to identify via energy minimization the ordered ground-state configurations of the molecules. We demonstrate the power of our approach by successfully reproducing, on a semiquantitative level, the intricate supramolecular ordering observed experimentally for PQP+ and ClO4- molecules at an Au(111)-electrolyte interface, including the formation of open-porous, self-host-guest, and stratified bilayer phases as a function of the electric field at the solid-liquid interface. We also discuss the role of the perchlorate ions in the self-assembly process, whose positions could not be identified in the related experimental investigations.

A Simply Synthesized, Tough Polyarylene with Transient Mechanochromic Response.

A simple and high-yielding route to tough polyarylenes of the type poly(meta,meta,para-phenylene) (PmmpP) is developed. PmmpP is tough even in its as-synthesized state which has an intermediate molar mass of Mw ≈60 kg mol-1 and exhibits outstanding mechanical properties at further optimized molecular weight of Mw =96 kg mol-1 , E=0.9 GPa, ϵ=300 %. Statistical copolymers with para,para-spiropyran (SP) are mechanochromic, and the toughness allows mechanochromism to be investigated. Strained samples instantaneously lose color upon force release. DFT calculations show this phenomenon to be caused by the PmmpP matrix that allows build-up of sufficiently large forces to be transduced to SP, and the relatively unstable corresponding merocyanine (MC) form arising from the aromatic co-monomer. MC units covalently incorporated into PmmpP show a drastically reduced half life time of 3.1 s compared to 4.5 h obtained for SP derivatives with common 6-nitro substitution.

Substituent Correlations Characterized by Hammett Constants in the Spiropyran-Merocyanine Transition.

The modification of molecular properties by the use of substituents is a versatile route for molecular design. Here we show for the example of multiresponsive spiropyrans that substituent effects and their correlations can be accurately described by Hammett constants, which in turn can be obtained directly from density functional theory calculations. The internal energetic difference ΔU between the noncolored and the colored form is determined for 63 spiropyran derivatives with substituents at the spiropyran N- and C6-positions, and can be described by only five parameters with an accuracy better than 0.1 eV (9.75 kJ/mol) using Hammett constants. This enables the prediction of ΔU values for other substituents without the need for further calculations nor experiments.