Polycationic Redox‐Active Cyclophanes with Integrated Electron‐Rich Diboron Units

Cationic cyclophanes are widely used in a variety of applications in supramolecular chemistry and materials science. In this work the authors systematically study the integration of electron‐rich diboron units with B(II) atoms into polycationic cyclophanes with viologen‐like electron‐acceptor units. They also report a first hexacationic cage‐compound in which three diboron units connect two tris(4‐pyridyl)triazine acceptor units. Moreover, di‐ and tetracationic open‐structure compounds, in which one diboron unit connects two bispyridyl groups, were synthesized and the properties compared to those of the corresponding closed structures (cyclophanes). The combination of diboron electron‐donor units and bi‐ or oligopyridyl electron‐acceptor units leads to intriguing optical and redox properties.