A Two‐Dimensional Supramolecular Framework Created by Cooperative Self‐Assembly

A 2D van der Waals supramolecular framework is created by self‐assembled crystallization of C 70 and decanethiol molecules on the Au(111) surface. This framework consists of C 70 dimer rows with decanethiol molecules filling the space between the dimer rows. The decanethiol “staple”, RS–Au–SR (R = CH 3 (CH 2 ) 9 ), acts as a spacer/binder that stabilizes the C 70 dimer rows and prevents the C 70 molecules from condensing into the usually close‐packed structure. The relatively weak van der Waals interaction plays a key role in such a cooperative self‐assembly process, where a regular stable structure is formed through the compromise between two competing building blocks.