Self-Assembly and Self-Organization of Self-Recognizing Cyclophanes

Abstract

An analysis is presented of the different contributions that give rise to the packing observed in the crystal structures of a wide range of bipyridinium-based molecular assemblies and supramolecular arrays. It is demonstrated how the various interactions – electrostatic, van der Waals, and π-π interactions – that contribute to the solid-state arrangement of these molecules and supermolecules can be utilized in order to design a series of tetracationic cyclophanes that can potentially self-organize in a highly ordered way in the solid state by virtue of the fact that they contain π-electron donors as well as π-electron acceptors. The syntheses of these cyclophanes is outlined and the tunability of the self-assembly methodology in their construction is demonstrated. One of these tetracationic cyclophanes – comprising π-electron-rich hydroquinone rings and π-electron-deficient bipyridinium units – has been shown to pack as highly ordered two-dimensional, mosaic-like sheets in the solid state. Its dicationic precursor also forms extended π-π-stacked layers in the solid state. An analogous cyclophane – containing two π-electron-rich resorcinol rings in place of the two hydroquinone rings – forms, in the solid state, one-dimensional arrays wherein the component resorcinol rings interact through their parallel π-π stacking. It has also been established that the first of the aforementioned tetracationic cyclophanes forms a 1:1 adduct with ferrocene in both the solution and solid states. X-ray crystallography, performed on the 1:1 adduct, reveals that not only is the ferrocene molecule complexed in a π-π stacking sense within the tetracationic cyclophane, but the 1:1 adduct also packs in a manner that is remarkably similar to the supramolecular organization of the free cyclophane in the crystalline state.