Designing the self‐assembly of disordered materials via color frustration

The ability to control self-assembly with atomic-level precision has led to remarkable advances in the rational design of crystalline materials. However, similar design strategies have yet to be developed for amorphous materials. Here, a strategy is devised for programming the self-assembly of amorphous structures by encoding frustration into the building block design. The building blocks are tailored to locally favor the formation of five-member rings and yield a network of face-sharing dodecahedral cages whose icosahedral symmetry prevents long-range order. Surprisingly, unlike geometrically frustrated glasses that form through kinetic arrest, the network nucleates spontaneously from the liquid phase, representing a novel type of thermodynamically stable disordered phase. The stabilization of this frustrated phase via programmable interactions paves the way for a new generation of disordered materials.