Pentagon, Hexagon, or Bridge? Identifying the Location of a Single Vanadium Cation on Buckminsterfullerene Surface

Buckminsterfullerene C₆₀ has received extensive research interest since its discovery. In addition to its interesting intrinsic properties of exceptional stability and electron-accepting ability, the broad chemical tunability by decoration or substitution on the C₆₀-fullerene surface makes it a fascinating molecule. However, to date, there is uncertainty about the binding location of such decorations on the C₆₀ surface, even for a single adsorbed metal atom. In this work, we report the gas-phase synthesis of the C₆₀V⁺ complex and its in situ characterization by mass spectrometry and infrared spectroscopy with the help of quantum chemical calculations and molecular dynamics simulations. We identify the most probable binding position of a vanadium cation on C₆₀ above a pentagon center in an η⁵-fashion, demonstrate a high thermal stability for this complex, and explore the bonding nature between C₆₀ and the vanadium cation, revealing that large orbital and electrostatic interactions lie at the origin of the stability of the η⁵-C₆₀V⁺ complex.