Light‐Induced Direct Arylation in the Solid Crystalline State as a Strategy Towards π‐Expanded Imidazoles

π‐Expanded imidazoles bearing the 2‐iodophenyl substituent at position 2 undergo direct photoinduced intramolecular arylation in the solid, crystalline state leading to large non‐planar heterocycles. An analogous reaction employing 2‐bromophenyl and 2‐chlorophenyl substituents is considerably slower. Such processes have never before been demonstrated to occur in crystals and have allowed the efficient synthesizes of structurally unique compounds containing either the phenanthro9′,10′:4,5]imidazo1,2‐f]phenanthridine moiety or structurally related skeletons. The reaction occurs in the thin crystalline layers irradiated with UV photons in an almost quantitative manner over 48–72 h. Several previously unknown architectures have been prepared using this methodology. Furthermore, the optical properties of these π‐expanded imidazoles can be altered with the addition of heteroatoms and/or electron‐donating groups.