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Interactions of neutral pyridine ligands and anionic benzoate ligands with the metalloporphyrin walls of M 6 L 3  nanocages (M = [(tmeda)Pt] 2+ , L = tetra(3-pyridyl)porphyrin-M′, M′ = Co II ,  Co 3 -1 ; Zn II ,  Zn 3 -1 ) were evaluated in CD 3 CN. The binding of ligands to simple tetra( N -methyl-3-pyridinium)porphyrin-M′ complexes  Co-2  and  Zn-2  was also evaluated. It was found that pyridine ligands bind with generally similar strength to the monomeric porphyrins as to the outer faces of the corresponding cage. Coordination is enhanced inside the cages for the binding of one equivalent of pyridine, 3-methylpyridine, or 3,5-dimethylpyridine. In contrast, 4-(4′-methoxyphenyl)pyridine cannot bind inside the cages, and 4-methylpyridine shows weaker binding inside than outside. Steric effects play a complex role in influencing ligand binding since 4- tert -butylpyridine binds more strongly in the cages than 4-methylpyridine. These latter two ligands also reveal a subtle allosteric effect in which binding of ligands inside  Zn 3 -1  becomes increasingly favored over external binding once some of the external sites are occupied. It was confirmed that benzoate and 3,5-di- tert -butylbenzoate can also coordinate to the walls of  M 3 -1 , but quantitative analysis of these interactions was complicated by competing affinity of the anions for other sites of the cages, limiting detailed insight.

Effects of a triangular nanocage structure on the binding of neutral and anionic ligands to Co II and Zn II porphyrins