Nanopatterns of molecular spoked wheels as giant homologues of benzene tricarboxylic acids.

Molecular spoked wheels with D 3h and C s symmetry are synthesized by Vollhardt trimerization of C 2v-symmetric dumbbell structures with central acetylene units and subsequent intramolecular ring closure. Scanning tunneling microscopy of the D 3h-symmetric species at the solid/liquid interface on graphite reveals triporous chiral honeycomb nanopatterns in which the alkoxy side chains dominate the packing over the carboxylic acid groups, which remain unpaired. In contrast, C s-symmetric isomers partially allow for pairing of the carboxylic acids, which therefore act as a probe for the reduced alkoxy chain nanopattern stabilization. This observation also reflects the adsorbate substrate symmetry mismatch, which leads to an increase of nanopattern complexity and unexpected templating of alkoxy side chains along the graphite armchair directions. State-of-the-art GFN-FF calculations confirm the overall structure of this packing and attribute the unusual side-chain orientation to a steric constraint in a confined environment. These calculations go far beyond conventional simple space-filling models and are therefore particularly suitable for this special case of molecular packing.

A Liquid-Crystalline Phenylene-Based Shape-Persistent Molecular Spoked Wheel.

Molecular spoked wheels with an all-phenylene backbone and different alkoxy side chain substitution patterns were synthesized using a cobalt-catalyzed [2 + 2 + 2] cycloaddition and subsequent template-directed cyclization via Yamamoto coupling. The two-dimensional organization of the molecules at the solid/liquid interface was investigated by means of scanning tunneling microscopy, allowing imaging of the molecular structure with submolecular resolution. With the right proportion of the flexible alkyl corona to the rigid core, mesomorphic behavior of one compound could be observed over a wide temperature range.

Evaluation of Cyclooctatetraene-Based Aliphatic Polymers as Battery Materials: Synthesis, Electrochemical, and Thermal Characterization Supported by DFT Calculations.

Organic electrode materials for rechargeable batteries are becoming a viable alternative for existing technologies. In particular, redox polymers have shown great performances. While many cathode-active derivatives are known, the development of their anode-active counterparts, required for the design of full-organic batteries, lacks behind. Here we present investigation on the suitability of cyclooctatetraene (COT)-based aliphatic polymers as anode-active battery materials, inspired by the known reversible reduction chemistry of COT at low electrochemical potential. We found that both synthesized polystyrene derivatives, side-group functionalized with COT, showed limited electrochemical reversibility of the reduction processes, whereas reductions proceeded reversibly in model compounds of these polymers. Differential scanning calorimetry measurements and density-functional theory calculations showed that this incomplete reversibility was due to cross-linking reactions occurring between COT units in the polymers. For the future of COT-based redox polymers, we propose a molecular design that prevents these cross-linking reactions.