Phthalocyanines (Pcs) have a wide variety of applications as colorants, photodynamic
therapeutics, photovoltaic materials, catalysts etc. Pcs tend to co-facially aggregate due to the π
– π interactions between their aromatic macrocycles, which may hinder certain applications. The
insertion of 2,6-di-iso-propylphenoxy substituents at the peripheral sites of the Pc [(dipPhO)8Pc]
proved successful in preventing aggregation between the macrocycles while the bulky
substituents created accessible voids towards the active metal centre. Upon crystallisation of
various metal (dipPhO)8Pc derivatives, clathrates with an interesting cubic structure, where the
volume occupied by the crystallisation solvent amounts to around 40% of the unit cell, were
obtained. Suitably sized bidentate ligands act as wall-ties to stabilise the crystal structure upon
removal of the solvents that otherwise would cause loss of crystallinity. We have found that there
is an astonishing range of metal cations, axial ligands and molecular wall-ties that are compatible
with the formation of the porous crystal. Preliminary data using a gas cell for the in-situ analysis
of O2, NO and CO binding to the metal cation will be reported. In addition, the co-crystallisation
of (dipPhO)8Pc with tetraphenyl porphyrin (H2TPP) and the in-situ incorporation of bidentate
ligands and of metals in the macrocycle of the TPP will be demonstrated
