Effect of asymmetry on frustrated crystallization

Abstract

Abstract Partial bonding in colloidal systems is often regarded as an obstacle to order, as it introduces geometric frustration. Yet, frustration can instead serve as a powerful design principle for controlling the formation of porous crystalline monolayers. By systematically varying the asymmetry in patch placement on anisotropic rhombic platelets, we investigate how partial bonding and geometric frustration can be tuned to direct polymorph selection, modulate porosity, and optimize crystal yield. This reveals an alternative route to crystallinity in patchy colloids – one that relies not on maximizing bonding, but on purposefully limiting it. Our findings establish a new strategy for programming functionality in colloidal materials, with relevance for the rational design of supramolecular architectures, DNA-based nanomaterials, and stimuli-responsive assemblies.