Two-dimensional supramolecular honeycomb networks with cavities of an internal diameter of 2.95 nm were formed by the self-assembly of 4,4',4' '-benzene-1,3,5-triyl-tribenzoic acid (BTA) on a Ag(111) surface at room temperature. Annealing to higher temperatures resulted in two sequential phase transformations into closer-packed supramolecular arrangements. The phase transformations are associated with stepwise deprotonation of the carboxylic acid groups. The voids of the honeycomb network of BTA have a suitable size for the construction of hierarchical structures with guest molecules. Single molecules of the macrocyclic compound mt-33 were successfully confined inside 2D nanocavities of the honeycomb networks and released when the phase was transformed to the close-packed structure.

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A marked difference is observed in the photochemistry of [2]catenanes containing a complexed ruthenium(II) center. The photochemical reactions result in a decoordination process and large amplitude motions through the formation of a strongly dissociative ligand‐field excited state (see example, L=CH3CN or Cl−), with the rate dependent on the ring size. The back reaction is performed thermally.