Mapping the Assembly of Metal-Organic Cages into Complex Coordination Networks.

Structural transformations of supramolecular assemblies play an important role in the synthesis of complex metal-organic materials. Nonetheless, often little is known of the assembly pathways that lead to the final product. This work describes the conversion of cubic metal-organic polyhedra to connected-cage networks of varying topologies. The neutral cubic cage assembly of formula {Pd3 [PO(NiPr)3 ]}8 (PZDC)12 has been synthesized from {Pd3 [(NiPr)3 PO](OAc)2 (OH)}2 ⋅2 (CH3 )2 SO and 2,5-pyrazenedicarboxilic acid (PZDC-2H). This 42-component self-assembly is the largest known among the neutral cages with PdII ions. The cage contains twenty-four vacant carboxylate O-sites at the PZDC ligands that are available for further coordination. Post-assembly reactions of the cubic cage with FeII and ZnII ions produced cage-connected networks of dia and qtz topologies, respectively. During these reactions, the discrete cubic cage transforms into a network of tetrahedral cages that are bridged by the 3D metal ions. The robustness of the [Pd3 {[PO(NiPr)3 }]3+ molecular building units made it possible to map the post-assembly reactions in detail, which revealed a variety of intermediate 1D and 2D cage networks. Such step-by-step mapping of the transformation of discrete cages to cage-connected frameworks is unprecedented in the chemistry of coordination driven assemblies.