No abstract

Self-assembly provides an attractive route to functional organic materials, with properties and hence performance depending sensitively on the organization of the molecular building blocks. Molecular organization is a direct consequence of the pathways involved in the supramolecular assembly process, which is more amenable to detailed study when using one-dimensional systems. In the case of protein fibrils, formation and growth have been attributed to complex aggregation pathways that go beyond traditional concepts of homogeneous and secondary nucleation events. The self-assembly of synthetic supramolecular polymers has also been studied and even modulated, but our quantitative understanding of the processes involved remains limited. Here we report time-resolved observations of the formation of supramolecular polymers from π-conjugated oligomers. Our kinetic experiments show the presence of a kinetically favoured metastable assembly that forms quickly but then transforms into the thermodynamically favoured form. Quantitative insight into the kinetic experiments was obtained from kinetic model calculations, which revealed two parallel and competing pathways leading to assemblies with opposite helicity. These insights prompt us to use a chiral tartaric acid as an auxiliary to change the thermodynamic preference of the assembly process. We find that we can force aggregation completely down the kinetically favoured pathway so that, on removal of the auxiliary, we obtain only metastable assemblies.

Hydrogen-bonded liquid crystalline polymers have emerged as promising “smart” supramolecular functional materials with stimuli-responsive, self-healing, and recyclable properties. The hydrogen bonds can either be used as chemically responsive (i.e., pH-responsive) or as dynamic structural (i.e., temperature-responsive) moieties. Responsiveness can be manifested as changes in shape, color, or porosity and as selective binding. The liquid crystalline self-organization gives the materials their unique responsive nanostructures. Typically, the materials used for actuators or optical materials are constructed using linear calamitic (rod-shaped) hydrogen-bonded complexes, while nanoporous materials are constructed from either calamitic or discotic (disk-shaped) complexes. The dynamic structural character of the hydrogen bond moieties can be used to construct self-healing and recyclable supramolecular materials. In this review, recent findings are summarized, and potential future applications are discussed.

The potential of liquid crystal polymers to undergo light-triggered shape changes makes them attractive for untethered bioinspired soft robots.