Trifluoroethoxy‐Coated Subphthalocyanines Attract Small Arenes in Their π‐Concave Cavity

AbstractX‐ray crystallographic analyses of a series of trifluoroethoxy‐substituted subphthalocyanines disclosed that a molecule of toluene is clasped at the center of the molecular concave cavity. Twelve trifluoroethoxy substituents, which flexibly surround the toluene molecule to hold it on the 14 π‐electron‐conjugated surface of the subphthalocyanines, can also catch a molecule of benzene. In contrast, a nonsubstituted subphthalocyanine does not show the same phenomena, and two subphthalocyanine units are required to maintain a small aromatic compound in their concave cavity. DFT calculations of the complexes were conducted to better understand the arene clathrates. Trifluoroethoxy‐substituted subphthalocyanines can be used to prepare arene clathrates as a result of their concave space. This is a unique approach to obtaining X‐ray crystal structures of small noncrystalline aromatic compounds.