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

TL;DR

This study combines experimental and computational methods to determine that a vanadium cation preferentially binds above a pentagon center on the C60 fullerene surface, revealing insights into its stability and bonding nature.

Contribution

It provides the first direct identification of the binding site of a single vanadium cation on C60, using mass spectrometry, spectroscopy, and quantum calculations.

Findings

Vanadium cation binds above a pentagon center in eta5-fashion

The C60V+ complex exhibits high thermal stability

Orbital and electrostatic interactions drive the stability

Abstract

Buckminsterfullerene C60 has received extensive research interest ever 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 in-frared 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 eta5-fashion, demonstrate a high thermal stability for this complex, and explore the bonding nature between C60 and the vanadium cation, reveal-ing that large orbital and electrostatic interactions lie at the origin of the stability of the eta5-C60V+ complex.