Trifluoroethoxy-Coated Subphthalocyanines Attract Small Arenes in Their π-Concave Cavity.

X-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.