Clathrates are open crystals in which molecules are arranged in a hierarchy of polyhedral cages that encapsulate guest molecules and ions. As well as holding fundamental interest, molecular clathrates serve practical purposes, such as for gas storage, and their colloidal counterparts also appear promising for host–guest applications. Here using Monte Carlo simulations, we report the entropy-driven self-assembly of hard truncated triangular bipyramids into seven different host–guest colloidal clathrate crystals with unit cells ranging from 84 to 364 particles. The structures consist of cages that are either empty or occupied by guest particles, which can be different from or identical to the host particles. The simulations point to crystallization occurring through the compartmentalization of entropy between low- and high-entropy subsystems for the host and the guest particles, respectively. We use entropic bonding theory to design host–guest colloidal clathrates with explicit interparticle attraction, providing a route to realize such systems in the laboratory.

包合物是开放晶体，其中分子排列在封装客体分子和离子的多面体笼的层次结构中。除了具有基本的兴趣外，分子包合物还具有实际用途，例如用于气体储存，而它们的胶体对应物也似乎在主客体应用中很有前景。在这里，我们使用蒙特卡罗模拟，报告了熵驱动的硬截断三角双锥体自组装成七种不同的主客体胶体包合物晶体，其晶胞范围从 84 到 364 个颗粒。这些结构由空的或被客体粒子占据的笼子组成，客体粒子可以与主体粒子不同或相同。模拟表明，通过分别在主体粒子和客体粒子的低熵子系统和高熵子系统之间划分熵而发生结晶。我们利用熵键合理论来设计具有明确颗粒间吸引力的主客体胶体包合物，为在实验室中实现此类系统提供了途径。