Tiara[5]arenes: Synthesis, Solid-State Conformational Studies, Host-Guest Properties, and Application as Nonporous Adaptive Crystals

Tiara[5]arenes (T[5]s), a new class of five-fold symmetric oligophenolic macrocycles that are not accessible from the addition of formaldehyde to phenol, were synthesized for the first time. These pillar[5]arene-derived structures display both unique conformational freedom, differing from that of pillararenes, with a rich blend of solid-state conformations and excellent host-guest interactions in solution. Finally we show how this novel macrocyclic scaffold can be functionalized in a variety of ways and used as functional crystalline materials to distinguish uniquely between benzene and cyclohexane.