A Full Spectrum of Disc‐Like Giant Molecular Geometry's Impacts on Self‐Assembled Soft Alloys

Abstract Complex metal alloy‐like superlattices constructed by soft matter (also known as soft alloys) have been widely reported. However, understanding the relationship between molecular geometry and resulting superlattices is still a fundamental challenge across a wide range of soft matter systems. In this work, the self‐assembly of disc‐like giant molecules (GMs) is systematically designed and explored with different peripheral crowdedness. As a result, a series of complex superlattices, including Frank‐Kasper A15, C15, σ phases as well as dodecagonal quasicrystal (DDQC) are observed. These results demonstrate that the size differences of mesoatoms in superlattices, which are intrinsically affected by disc‐like giant molecular peripheric crowdedness, plays a significant role in the formation of these complex superlattices. With this insight, a protocol for engineering disc‐like giant molecular geometries is proposed to rationally fabricate soft alloys. This work pioneers a new avenue for constructing complex superlattices through rational molecular geometry design.