Partially Bonded Crystals: A Pathway to Porosity and Polymorphism

In recent years, experimental and theoretical investigations have shown that anisotropic colloids can self-organize into ordered porous monolayers, where the interplay of localized bonding sites, so-called patches, with the particle's shape is responsible for driving the systems away from close-packing and toward porosity. Until now it has been assumed that patchy particles have to be fully bonded with their neighboring particles for crystals to form, and that, if full bonding cannot be achieved due to the choice of patch placement, disordered assemblies will form instead. In contrast, we show that by deliberately displacing the patches such that full bonding is disfavored, a different route to porous crystalline monolayers emerges, where geometric frustration and partial bonding are decisive process. The resulting dangling bonds lead to the emergence of effectively chiral units which then act as building blocks for energetically equivalent crystal polymorphs.