It was of interest to determine whether the incorporation of TPP helps to stabilise the PNC structure towards the removal of included solvent. Encouragingly, crystals of PNC[H 2 /vTPP] left to dry under ambient conditions retained crystalline order as confirmed by scXRD analysis, which showed that both the cell volume had increased by 2.5% and that the angle of curvature of the (dipPhO) 8 PcH 2 component had decrease by 4° relative to values for the solvated crystal. However, these unsolvated crystals did not demonstrate permanent porosity by nitrogen adsorption at 77K and it is possible that the rigorous degassing protocol used prior to analysis removed some remaining solvent that is crucial for structural stability. In order to attain permanent porosity for the PNC[M/vTPP] co-crystals, stabilisation using molecular "wall-ties" was attempted by the introduction of a bidentate ligand into PNC[cH 2 O-Co/vTPP]. This was readily achieved by adding 4,4'-bipyridyl into the methanol solvent in contact with the crystals with 100% incorporation of the wall-tie ligands into the cavity to give PNC[vTPP/Co-cbipy-Co/vTPP] as confirmed by scXRD. Removal of included solvent from these crystals to give did not result in loss of order and only a slight reduction in unit cell volume (0.4%). Nitrogen adsorption analysis at 77K of PUNC[vTPP/Co-cbipy-Co/vTPP] showed significant uptake at low relative pressure to give a typical Type 1 isotherm shape consistent with a microporous material (Fig. ). This data was used to calculate a Brunauer-Emmett-Teller surface area (SABET) of 454 m 2 g -1 and a micropore volume (V mp ) of 0.22 ml g -1 . Direct comparison of this N 2 adsorption data with that of the previously prepared PUNC[Co-cbipy-Co] (Fig. ; SABET = 845, V mp = 0.44 ml g -1 ) indicates that the TPP guest molecules occupy around 50% of the free volume of the basic PNC structure (Fig. ). The modest uptake of CO2 at 273K by PUNC[vTPP/Co-cbipy-Co/vTPP] (Fig. ) suggests that only a small fraction of the total pore volume is distributed as ultramicropores, defined as pores of less than 7 Å in diameter, which is consistent with the crystal structure of the PNC, for which only the narrow channels linking the voids are ultramicroporous. Notably, the CO2 uptake for PUNC[vTPP/Co-cbipy-Co/vTPP] is significantly higher than that of PUNC[Co-cbipy-Co], which is consistent with the increase in ultramicroporosity due to the included TPP increasing the length of the narrow interconnecting channels from ~9 Å to ~15 Å, as measured from the scXRD structure. The resulting permanently porous PUNC[vTPP/Cocbipy-Co/vTPP] possesses metal-free porphyrins suitable for metal cation incorporation via postsynthetic modification. Hence the crystals were exposed to a methanol solution of CuCl2 and the successful in-situ incorporation of Cu 2+ to give PNC[vTPPCu/Co-cbipy-Co/vTPPCu] was confirmed by scXRD, which showed that the resulting Cu-Co distance is only 3.51 Å. Similarly, Co 2+ could be introduced into the TPP by exposure to a solution of CoCl2 to produce PNC[vH2OCoTPP/Co-cbipy-Co/vTPPCo-OH2] with a Co-Co distance of 3.52 Å. The efficient incorporation of TPP within PNCs creates structurally complex porous materials from two easily prepared, multifunctional precursors by simple co-crystallisation. These cocrystals add to the structural diversity of the PNC system and provide further evidence of the remarkable ability of (dipPhO) 8 PcM to direct crystal formation using only weak and non-directional molecular interactions. The TPP/PNC structure offers two distinct sites for metal cation incorporation that can be filled either with the same or different cations, depending on the (dipPhO) 8 PcM and TPPM components used for crystal formation, or by post-crystallisation treatment of metal-free macrocycles with the appropriate metal salts. Both metal sites are accessible to reactants of moderate size such as small organic molecules and gases, as demonstrated by the addition of wallties, such as 4,4'-bipyridyl, which stabilise the structure towards the complete removal of included solvent and by gas adsorption, respectively. Therefore, guided by the results from the extensive research on the use of metal-containing porphyrins and phthalocyanines as homogeneous catalysts and photocatalysts, the porous PNC/TPP co-crystals will allow the design and straightforward construction of novel heterogeneous catalysis. Of particular interest would be cooperative or tandem reactions in which there is synergy between the two adjacent metals within the PNC/TPP co-crystals, for example, one metal cation helping to stabilise a reactive catalytic state on the adjacent macrocycle. In addition, photocatalysis may benefit from the complementary light-harvesting achieved by the porphyrin/phthalocyanine heterodimer across the visible spectrum.