Secondary Bracing Ligands Drive Heteroleptic Cuboctahedral Pd(II)(12) Cage Formation

[Image: see text] The structural complexity of self-assembled metal–organic capsules can be increased by incorporating two or more different ligands into a single discrete product. Such complexity can be useful, by enabling larger, less-symmetrical, or more guests to be bound. Here we describe a rational design strategy for the use of subcomponent self-assembly to selectively prepare a heteroleptic cage with a large cavity volume (2631 Å(3)) from simple, commercially available starting materials. Our strategy involves the initial isolation of a tris(iminopyridyl) Pd(II(3)) complex 1, which reacts with tris(pyridyl)triazine ligand 2 to form a heteroleptic sandwich-like architecture 3. The tris(iminopyridyl) ligand within 3 serves as a “brace” to control the orientations of the labile coordination sites on the Pd(II) centers. Self-assembly of 3 with additional 2 was thus directed to generate a large Pd(II(12)) heteroleptic cuboctahedron host. This new cuboctahedron was observed to bind multiple polycyclic aromatic hydrocarbon guests simultaneously.