Tetrahomo corona[4]arene-based spirophanes: synthesis, structure, and properties

In contrast to a plethora of macrocyclic and cage compounds, spirophanes have remained largely unexplored. We report herein the construction, structure and properties of unprecedented tetrahomo corona[4]arene-based ditopic and tritopic macrocycles of spiro structures. Synthesis was conveniently achieved by means of an efficient S N Ar reaction from simple and commercially available starting materials. Racemic samples were resolved into enantiopure chiral tetrahomo i -corona[4]arenes, spirophanes and bispirophanes which show interesting chiroptical properties. The acquired electron-deficient macrocyclic compounds were found to adopt unique conformational structures and to form distinct complexes with TTF in the solid state. Our study provides a new opportunity to develop multitopic macrocycles of different topologies which have potential applications in supramolecular chemistry. Racemic and enantiopure spirophanes and bispirophanes consisting of orthogonally configured tetrahomo corona[4]arene and i -corona[4]arene macrocycles were obtained and they displayed interesting tetrathiafulvalene binding and chiroptical properties.