Porous Molecular Crystals Derived from Cofacial Porphyrin/Phthalocyanine Heterodimers.

Porphyrin‐based porous materials are of growing interest as heterogeneous catalysts especially for reactions that are of importance to sustainability. Here we demonstrate that porous molecular crystals can be prepared by the simple co‐crystallisation of tetraphenylporphyrin (TPP) with octa(2’,6’‐di‐<italic>iso</italic>‐propylphenoxy)phthalocyanine or some of its metal complexes [(dipPhO)8PcM; M=H2, Al−OH, Ti=O, Mn−Cl, Fe−Cl, Co, Ni, Cu, Zn, Ga−Cl, Ag, In−Cl or Au−Cl]. This process is facilitated by the efficient formation of the supramolecular heterodimer between TPP and (dipPhO)8PcM, which is driven by the complementary shape and symmetry of the two macrocycles. The (dipPhO)8PcM component directs the crystal structure of the heterodimers to form Phthalocyanine Nanoporous Crystals (PNCs) of similar structure to those formed by (dipPhO)8PcM alone. The incorporation of TPP appears to partially stabilise the PNCs towards the removal of included solvent and for cocrystals containing (dipPhO)8PcCo stability can be enhanced further by the <italic>insitu</italic> addition of 4,4‐bipyridyl to act as a “molecular wall tie”. These stabilised PNC/TPP cocrystals have a Brunauer–Emmett–Teller surface area (<italic>SABET</italic>) of 454 m2 g−1 and a micropore volume (<italic>Vmp</italic>) of 0.22 mL g−1. The reactivity of both macrocycles within the PNC/TPP co‐crystals is demonstrated by <italic>insitu</italic> metal insertion. [ABSTRACT FROM AUTHOR]