Negative and positive anisotropic thermal expansion in 2D fullerene networks

We find a design principle for tailoring thermal expansion properties in nearly-spherical molecular networks. Using 2D fullerene networks as a representative system, we realize positive thermal expansion along intermolecular [2\,+\,2] cycloaddition bonds and negative thermal expansion along intermolecular C$-$C single bonds by varying the structural frameworks of molecules. The microscopic mechanism originates from a combination of the framework's geometric flexibility and its transverse vibrational characteristics. Based on this insight, we find molecular networks beyond C$_{60}$ with tunable thermal expansion. These findings shed light on the fundamental mechanisms governing thermal expansion in molecular networks towards rational materials design.