Low-Symmetry MOF-Based Patchy Colloids and Their Precise Linking via Site-Selective Liquid Bridging to Form Supra-Colloidal and Supra-Framework Architectures.

Colloids with surface patches (or patchy particles) can bind and assemble with directionality. However, the bonding between the usually high-symmetry, dome-shaped patches is not precise, as it cannot lock the exact position and orientation of the relevant particles. This issue prevents the assembly of well-defined colloidal superstructures by design. Herein, we introduce low-symmetry, metal-organic framework (MOF)-based patchy colloids, which feature a polyhedral matrix and flat hexagonal patches, along with anisotropic surfaces and compositions. Guided by the encoded shape/chemical information and mediated by a site-selective liquid-bridging interaction, the distinct patchy particles self-assemble into supra-colloidal (or supra-framework) structures with unprecedented precision. In this case, the valence, position, and orientation of the particles within assemblies are fully coordinated and precisely aligned. The dynamic nature of the liquid bridges also allows us to investigate the unique assembly kinetics. Our strategy not only defines new modes of colloidal bonding, but also provides a powerful means toward creating hierarchical and multi-component MOF materials.