Rational Design and Construction of Hierarchical Superstructures Using Shape-Persistent Organic Cages: Porphyrin Box-Based Metallosupramolecular Assemblies.

We report a new approach to building hierarchical superstructures using a shape-persistent porous organic cage, which acts as a premade secondary building unit, and coordination chemistry. To illustrate the principle, a zinc-metalated porphyrin box (Zn-PB), a corner-truncated cubic porous cage, was connected by suitable dipyridyl terminated bridging ligands to construct PB-based hierarchical superstructures (PSSs). The PSSs were stabilized not only by the coordination bonds between Zn ions and bipyridyl-terminated ligands but also by π-π interactions between the corners of the Zn-PB units. By varying the length of the linker, we identified an optimum range of the linker length for construction of PSSs. The PSSs have large void volumes and an extrinsic surface area compared to the parent PBs, which can be exploited for the selective encapsulation and interior functionalization of the PSSs for various applications, including catalysis. We observed that singlet oxygen induced synthesis of the natural product, juglone, is more efficiently catalyzed by PSS-1 than its constituent component Zn-PB.