Construction and charge-transfer complexation of adamantane-based macrocycles and a cage with aromatic ring moieties.

Adamantane-based macrocycles and a cage with aromatic ring moieties have been developed and structurally revealed by X-ray crystallographic analysis. The dimerized (1) and trimerized (2) macrocycles of binary molecules based on adamantane with acetylenic aromatic ring moieties were designed and effectively synthesized. Similarly, a cryptand-like macrobicyclic cage (3) was constructed from a trisubstituted adamantane derivative. Single-crystal X-ray analysis revealed that both cyclic compounds have nearly a rectangular shape with or without a solvent molecule in the cavity. The macrobicyclic cage has an inner space and accommodates a chloroform molecule via C-H...pi interactions. Macrocycles and cage encapsulate 1,3,5-trinitrobenzene (4) as an electron-poor guest in a one-to-one complex via charge-transfer interactions in a parallel fashion, and showed the formation of molecular networks such as columns, tubes, 2D layers, and 3D networks composed of two different types through noncovalent interactions in the solid state.