Gas‐phase complexes of [n]helicenes with n = 6 ‐ 8 and the silver(I) cation are generated utilizing electrospray ionization mass spectrometry (ESI‐MS). Besides the well‐established [1:1] helicene/Ag+‐complex in which the helicene provides a tweezer‐like surrounding for the Ag+, there is also a [2:1] complex formed. Density‐functional theory (DFT) in conjunction with energy‐resolved collision‐induced dissociation (ER‐CID) experiments reveal that the second helicene attaches via π‐π stacking to the first helicene which is part of the pre‐formed [1:1] tweezer complex with Ag+. For polycyclic aromatic hydrocarbons (PAHs) of planar structure, the [2:1] complex with silver(I) is typically structured as a Ag+‐bound dimer (PAH‐‐‐Ag+‐‐‐PAH). For helicenes, the Ag+‐bound dimer is of similar thermochemical stability as the π‐π stacked dimer, however, it is kinetically inaccessible. Coronene (Cor) is investigated in comparison as an essentially planar PAH. In analogy to the π‐π stacked dimer of the helicenes, the Cor‐‐‐Ag+‐‐‐Cor‐‐‐Cor complex is also observed. Competition experiments using [n]helicene mixtures reveal that the tweezer complexes of Ag+ are preferably formed with the larger helicenes, with n = 6 being entirely ignored as the host for Ag+ in the presence of n = 7 or 8.

Stable radical cation π-dimers of superhelicenes are produced by ESI-MS. Dissociation into two singly charged ions is investigated using energy-resolved collision experiments. DFT calculations show the preferred formation of the open-shell dication.