Fullerene ion chemistry: a journey of discovery and achievement.

An account is provided of the extraordinary features of buckminster fullerene cations and their chemistry that we discovered in our Ion Chemistry Laboratory at York University (Canada) during a 'golden' period of research in the early 1990s, just after C60 powder became available. We identified new chemical ways of C60 ionization and tracked novel chemistry of C60 (n+) as a function of charge state (n=1-3) with some 50 different reagent molecules. We found that multiple charges enhance reaction rates and diversify reaction products and mechanisms. Strong electrostatic interactions with reagent molecules were seen to reduce barriers to carbon surface bonding and charge-separation reactions, while intramolecular Coulomb repulsion appeared to localize charge on the surface or the substituent and so influence higher order chemistry, including 'spindle', 'star', 'fuzzy ball', 'ball-and-chain' and dimer ion formation. We introduced the notion of 'apparent' gas-phase acidity with measurements of proton-transfer reactions of multiply charged fullerene cations. We also explored the attachment of atomic metal cations to C60 and their subsequent reactions. All these findings were applied to the possible chemistry of fullerene cations in the interstellar medium with a focus on multiply charged fullerene ion formation and the intervention of fullerene cations in fullerene derivatization and molecular synthesis, with a view to their possible future detection.This article is part of the themed issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene'.