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

Buckminsterfullerene C 60 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 C 60 -fullerene surface makes it a fascinating molecule. However, to date, there is uncertainty about the binding location of such decorations on the C 60 surface, even for a single adsorbed metal atom. In this work, we report the gas-phase synthesis of the C 60 V + 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 C 60 above a pentagon center in an η 5 -fashion, demonstrate a high thermal stability for this complex, and explore the bonding nature between C 60 and the vanadium cation, revealing that large orbital and electrostatic interactions lie at the origin of the stability of the η 5 -C 60 V + complex.