Halogen-Bond-Templated [2+2] Photodimerization in the Solid State: Directed Synthesis and Rare Self-Inclusion of a Halogenated Product

A ditopic halogen‐bond acceptor organizes a diiodooctafluorostilbene for a [2+2] photodimerization reaction to take place between two stilbene molecules in the solid state. The resultant cyclobutane product is functionalized with halogen atoms and undergoes self‐assembly to form a channel‐type host–guest compound that exhibits a very rare form of self‐inclusion. This way, please: A ditopic halogen‐bond acceptor organizes a halogenated stilbene for a stereoselective [2+2] photodimerization reaction to take place between two stilbenes in the solid state. The resultant halogen‐functionalized cyclobutane product self‐assembles to form a host–guest compound that exhibits a very rare form of self‐inclusion. Atom colors: C=gray; I=purple; N=blue; F=green.