Abstract
Crownphyrins are hybrid macrocycles combining structural features of porphyrin and crown ethers. The molecular architecture renders them an intriguing class of hosts capable of binding neutral, and ionic guests. The presence of dynamic covalent imine linkages connecting the dipyrrin segment with the ether chain enables unusual coordination behavior of crownphyrins, as demonstrated by the formation of two classes of strikingly different complexes. The remarkable metal-mediated expansion to the helical [2+2] macrocyclic complex is reversible. The reaction of the figure-eight mercury(II) assembly with [2.2.2]cryptand results in ring contraction providing the metal-free crownphyrin macrocycle.