Phototransformation of Stilbene in van der Waals Nanocapsules

We have utilized para‐hexanoylcalix[4]arene nanocapsules as hosts to carry out phototransformations of cis‐ and trans‐stilbene. Single‐crystal X‐ray diffraction studies were performed to define precisely the location of encapsulated stilbenes inside the capsule and to analyze possible pathways of phototransformation. cis‐Stilbene stacks as a π–π dimer located at the center of the capsule, whereas trans‐stilbene does not form such a dimer. Irradiation of the crystalline inclusion complexes of each isomer of stilbene in the solid state leads to the appearance of the second isomer, and after prolonged photolysis, photodimerization also occurs. syn‐Tetraphenylcyclobutane is formed as the major product of dimerization and its yield depends on the time and intensity of irradiation. In most cases, the single crystals of the complexes remain intact during irradiation; hence, the nanocapsules have the potential to serve as robust nanoreactors in the solid state. The confinement in the nanocapsules is sufficient to keep the reacting molecules together, although this is less restrictive than for trans‐stilbene crystals, in which the molecules cannot achieve a favorable orientation for dimerization.