A new type of porphyrin array has been synthesized by the coupling of six porphyrin moieties to a central benzene core via an ether linkage. The resulting porphryin supermolecule has a diameter up to 80 Å and a mass of 8500 daltons. In solution, the six porphyrins around the central benzene ring arrange themselves into three sets of offset overlapping dimers, which are rapidly interconverting at room temperature. Solution UV-vis and fluorescence studies, however, indicate that there are no electronic interactions between the individual porphyrin molecules. Upon spreading a chloroform solution of these porphyrin molecules on a surface, they self-assemble to form ring-shaped architectures on a micrometer scale. Near-field scanning optical microscopy studies reveal that the porphyrin moieties within the rings have an ordered arrangement with respect to their position in the ring after the sample has been annealed at 80 °C for 2 days.

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A series of multi‐porphyrin arrays were synthesized and the self‐assembly behaviour of these compounds at the air–water interface was investigated by the Langmuir–Blodgett technique. It was found that as the overall area of the porphyrin molecules was increased, upon going from a mono‐ to bis‐ to a tetra‐ and then to hexaporphyrin species, the intermolecular stacking between the molecules also increases, resulting in more stable monolayers. In the case of the hexaporphyrin species the intermolecular interactions are so strong that monolayer formation is irreversible. All porphyrin monolayers can be transferred to a glass surface with good transfer ratios, leading to highly ordered porphyrin films in which the chromophores are arranged orthogonal to the glass surface. Copyright © 2001 John Wiley & Sons, Ltd.

In this paper allosteric interactions are employed to enhance electron transfer in a pseudorotaxane system. Binding of an axial ligand (tbpy) to an electron donating mono-cavity appended zinc porphyrin (ZnP) increases the complexation strength to an electron accepting monosubstituted bipyridine, resulting in a more pronounced electron transfer process after excitation of the zinc porphyrin. Binding constants are presented for this host and different mono-substituted bipyridine guests.

Hexakis Porphyrinato Benzenes. A New Class of Porphyrin Arrays. --(BIEMANS, H. A. M.; ROWAN, A. E.; VERHOEVEN, A.; VANOPPEN, P.; LATTERINI, L.; FOEKEMA, J.; SCHENNING, A. P. H. J.; MEIJER, E. W.; DE SCHRYVER, F. C.; NOLTE, R. J. M.; J. Am. Chem.