Triamine and Tetramine Edge-Length Matching Drives Heteroleptic Triangular and Tetragonal Prism Assembly.

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Heteroleptic metal-organic capsules, which incorporate more than one type of ligand, can provide enclosed, anisotropic interior cavities for binding low-symmetry molecules of biological and industrial importance. However, the selective self-assembly of a single mixed-ligand architecture, as opposed to the numerous other possible self-assembly outcomes, remains a challenge. Here, we develop a design strategy for the subcomponent self-assembly of heteroleptic metal-organic architectures with anisotropic internal void spaces. Zn6Tet3Tri2 triangular prismatic and Zn8Tet2Tet'4 tetragonal prismatic architectures were prepared through careful matching of the side lengths of the tritopic (Tri) or tetratopic (Tet, Tet') and panels.