Self-limiting states of polar misfits: frustrated assembly of warped-jigsaw particles.

Abstract

We study the ground state thermodynamics of a model class of geometrically frustrated assemblies, known as warped-jigsaw particles. While it is known that frustration in soft matter assemblies has the ability to propagate up to mesoscopic, multi-particle size scales, notably through the selection of the self-limiting domain, little is understood about how the symmetry of shape-misfit at the particle scale influences emergent morphologies at the mesoscale. Here we show that polarity in the shape-misfit of warped-jigsaw puzzles manifests at a larger scale in the morphology and thermodynamics of the ground-state assembly of self-limiting domains. We use a combination of continuum theory and discrete particle simulations to show that the polar misfit gives rise to two mesoscopically distinct polar, self-limiting ribbon domains. Thermodynamic selection between the two ribbon morphologies is controlled by a combination of the binding anisotropy along distinct neighbor directions and the orientation of polar shape-misfit. These predictions are valuable as design features for ongoing efforts to program self-limiting assemblies through the synthesis of intentionally frustrated particles, further suggesting a generic classification of frustrated assembly behavior in terms of the relative symmetries of shape-misfit and the underlying long-range inter-particle order it frustrates.