Anisotropic Hierarchical Assembly of C ₆₀ from One Dimensional to Three Dimensional via Thiolate‐Mediated van der Waals Epitaxy

The anisotropic growth of C 60 is essential for engineering oriented electronic properties. This growth mode, however, is challenged by the strong thermodynamic drive of molecules forming close‐packed assemblies. This study demonstrates a thiolate‐mediated van der Waals (vdW) epitaxial strategy to construct C 60 anisotropic architectures with tunable dimensionality on Au(111). Using pentanethiol (PT) as a cohost species, we achieved precise structural control from 1D C 60 nanochains to 3D superstructures with an orthorhombic lattice. The directional diffusion of C 60 was engineered by controlling the assembly of PT molecules into striped or disordered phases. Striped PT template favors 1D growth of C 60 chains along the axis via anisotropic molecular channels, whereas disordered PT phase promotes the formation of 2D islands with rectangular lattices. The RS‐Au‐SR (R = CH 3 (CH 2 ) 4 SH) staple motifs act as quantized spacers and linkers between C 60 nanochains, which suppress close‐packing and enables the formation of a rectangular C 60 bilayer via vdW epitaxy. Interestingly, the third C 60 layer undergoes a phase transition to hexagonal close‐packing, indicating attenuation of the templating effect with increasing layer thickness. This work provides a synergistic molecular guidance approach for designing novel C 60 nanostructures with controllable dimensions, demonstrating potential for the precise construction of carbon‐based nanostructures and paving the way for future applications in molecular electronics.