One-Step Synthesis of Cyclophanes as Crystalline Sponge and Their [2]Catenanes through SN Ar Reactions.

This work reports that cyclophanes and their [2]catenanes were synthesized by the SN Ar reactions of disubstituted adamantanes bearing halophenol units and 3,6-dichlorotetrazine in moderate yields. In the crystalline state, the cyclophanes had hexagonal structures with a cavity. The [2]catenanes were composed of two macrocycles that were singly interlocked and orthogonally arranged, indicating the construction from eight component molecules through eight C-O bonds in a one-step reaction in up to 33 % yield. The cyclophanes were assembled to afford a supramolecular organic framework in the solid state, which exhibited permanent intrinsic porosity and adsorption of leaf alcohol or aldehyde in a single-crystal to single-crystal fashion. The molecular structures of the liquid guests were determined by single-crystal X-ray analysis. The formation of catenanes and the use of cyclophane-based porous crystals in the crystalline sponge method may be largely ascribed to the solvophobic effects and the van der Waals interactions that originate in the aliphatic and bulky nature of the adamantane units.