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A systematic investigation of the effect that simple substituents attached to the phenolic ring have on the stability and adsorption properties of the porous crystals of parent Sn(IV) porphyrin diphenolates is made. A family of three dimensional honey-comb-like supramolecular porous materials (SPMs) was obtained by crystallisation of three different discrete porphyrin diphenolates Sn(IV)tTTP(o-cresol)2 (1), Sn(IV)tTTP(o-bromo)2 (2), Sn(IV)tTTP(m-nitro)2 (3). Their structures and crystalline integrity were studied using single crystal X-ray diffraction and powder X-ray diffraction techniques, respectively. Vapor adsorption measurements on Sn(IV)tTTP(o-cresol)2 revealed a guest uptake capacity. Gas adsorption investigations of these materials demonstrates that this class of SPMs retains high thermal stability and permanent porosity with functional groups lining the pores, which makes this Sn(IV) porphyrin diphenolates family a potential candidate for building high thermal stability SPMs.

Three robust molecular porous materials (MPMs) constructed from Sn(IV)TTP(bisphenolates) were reported. They all possess 1D hourglass-shaped channels within their crystal structures. Functionalisation of the channel lining through judicial choice of substituted phenol was demonstrated, which also allowed for a change in the pore diameter. TGA investigations revealed that these novel supramolecular systems are thermally stable over 550 K.

The supramolecular assembly formed in the solid-state by the interaction of dihydroxy tin(IV) tetra(4-pyridyl)porphyrin (TPyP) with water is discussed. The resulting pseudo two-dimensional array of water molecules are ordered into helical chains by hydrogen bonding between neighboring water molecules along the chain as well as hydrogen bonding between water molecules and the axial hydroxyl and pyridyl groups of the tin(IV) porphyrin.