Site‐Specific Reduction‐Induced Hydrogenation of a Helical Bilayer Nanographene with K and Rb Metals: Electron Multiaddition and Selective Rb+ Complexation.

The chemical reduction of π‐conjugated bilayer nanographene 1 (C138H120) with K and Rb in the presence of 18‐crown‐6 affords [K+(18‐crown‐6)(THF)2][{K+(18‐crown‐6)}2(THF)0.5][C138H1223−] (2) and [Rb+(18‐crown‐6)2][{Rb+(18‐crown‐6)}2(C138H1223−)] (3). Whereas K+ cations are fully solvent‐separated from the trianionic core thus affording a "naked" 1.3− anion, Rb+ cations are coordinated to the negatively charged layers of 1.3−. According to DFT calculations, the localization of the first two electrons in the helicene moiety leads to an unprecedented site‐specific hydrogenation process at the carbon atoms located on the edge of the helicene backbone. This uncommon reduction‐induced site‐specific hydrogenation provokes dramatic changes in the (electronic) structure of 1 as the helicene backbone becomes more compressed and twisted upon chemical reduction, which results in a clear slippage of the bilayers. [ABSTRACT FROM AUTHOR]