Template-Assisted Proximity for Oligomerization of Fullerenes.

Demonstrated herein is an unprecedented porous template-assisted reaction at the solid-liquid interface involving bond formation, which is typically collision-driven and occurs in the solution and gas phases. The template is a TMA (trimesic acid) monolayer with two-dimensional pores that host fullerenes, which otherwise exhibit an insignificant affinity to an undecorated graphite substrate. The confinement of C-84 units in the TMA pores formulates a proximity that is ideal for bond formation. The oligomerization of C-84 is triggered by an electric pulse via a scanning tunneling microscope tip. The spacing between C-84 moieties becomes 1.4 nm, which is larger than the edge-to-edge diameter of 1.1-1.2 nm of C-84 due to the formation of intermolecular single bonds. In addition, the characteristic mass-to-charge ratios of dupers and trimers are observed by mass spectrometry. The experimental findings shed light on the active role of spatially tailored templates in facilitating the chemical activity of guest molecules.