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Self‐Assembly and Self‐Organization of Self‐Recognizing Cyclophanes
Author(s) -
Ashton Peter R.,
Chemin Alexandre,
Claessens Christian G.,
Menzer Stephan,
Stoddart J. Fraser,
White Andrew J. P.,
Williams David J.
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199806)1998:6<969::aid-ejoc969>3.0.co;2-g
Subject(s) - cyclophane , chemistry , ferrocene , supramolecular chemistry , stacking , crystallography , adduct , hydroquinone , molecule , synthon , stereochemistry , crystal structure , organic chemistry , electrochemistry , electrode
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.