Unique Supramolecular Liquid‐Crystal Phases with Different Two‐Dimensional Crystal Layers

We report herein a series of tetrablock‐mimic azobenzene‐containing [60]fullerene dyads that form supramolecular liquid crystals (LCs) from phase‐segregated two‐dimensional (2D) crystals. The unique double‐, triple‐, and quadruple‐layer packing structure of fullerenes in the 2D crystals leads to different smectic supramolecular LC phases, and novel LC phase transitions were observed upon changes in the fullerene packing layer number in the 2D crystals. Interestingly, by combining the LC properties with 2D crystals, these materials show excellent electron mobility in the order of 10⁻³ cm² V⁻¹ s⁻¹, despite their relatively low fullerene content. Our results provide a novel method to manipulate 2D crystal layer thickness, with promising applications in optoelectronic devices.