Functionalized corannulene carbocations: a structural overview

A detailed structural overview of a family of bowl-shaped polycyclic aromatic carbocations of the type [C20 H10 R](+) with different R functionalities tethered to the interior surface of corannulene (C20 H10 ) is provided. Changing the identity of the surface-bound groups through alkyl chains spanning from one to four carbon atoms and incorporating a different degree of halogenation has led to the fine tuning of the bowl structures and properties. The deformation of the corannulene core upon functionalization has been revealed based on X-ray crystallographic analysis and compared for the series of cations with R=CH3 , CH2 Cl, CHCl2 , CCl3 , CH2 CH3 , CH2 CH2 Cl, and CH2 CH2 Br. The resulting carbocations have been isolated with several metal-based counterions, varying in size and coordinating abilities ([AlCl4 ](-) , [AlBr4 ](-) , [(SnCl)(GaCl4 )2 ](-) , and [Al(OC(CF3 )3 )4 ](-) ). A variety of aggregation patterns in the solid state has been revealed based on different intermolecular interactions ranging from cation-anion to π-π stacking and to halogen⋅⋅⋅π interactions. For the [C20 H10 CH2 Cl](+) ion crystallized with several different counterions, the conformation of the R group attached to the central five-membered ring of corannulene moiety was found to depend on the solid-state environment defined by the identity of anions. Solution NMR and UV/Vis investigations have been used to complement the X-ray diffraction studies for this series of corannulene-based cations and to demonstrate their different association patterns with the solvent molecules.