A molecular Popeye: Li ⁺ @C ₆₀ and its complexes with [ n ]cycloparaphenylenes

In this work, we compare for the first time the stability of [n]cycloparaphenylene ([n]CPP)-based host-guest complexes with Li⁺@C₆₀ and C₆₀ in the gas and the solution phase. Our gas-phase experiments reveal a significant increase in stability for the complexes featuring [9-12]CPP with Li⁺@C₆₀. This increased interaction strength is also observed in solution. Isothermal titration calorimetry shows for the formation of [10]CPP⊃Li⁺@C₆₀ a two orders of magnitude larger association constant than that for the C₆₀ analog. Additionally, an increased binding entropy is observed. This study contributes to a better understanding of host-guest complexes between [n]CPPs and endohedral metallofullerenes at a molecular level, which is the prerequisite for future applications.