Precisely Constructing\nSuperlattices of Soft Giant\nMolecules via Regulating Volume Asymmetry

Soft matters, particularly giant molecular self-assembly,\nhave\nsuccessfully replicated complex structures previously exclusive to\nmetal alloys. These superlattices are constructed from mesoatomssupramolecular\nspherical motifs of aggregated molecules, and the formation of superlattices\ncritically depends on the volume distributions of these mesoatoms.\nHerein, we introduce two general methods to control volume asymmetry\n(i.e., the volumes’ ratio of the largest to smallest mesoatoms, <i>V</i><sub><i>L</i></sub><i>/V</i><sub><i>S</i></sub>) within giant molecular self-assembly. Leveraging\nthe spontaneous increase in the mesoatomic volume ratio in unary systems\nand self-sorted binary blends, we systematically adjust the volume\nasymmetry from 1.0 to 9.0 across 24 unary systems and 56 binary blends\nof giant molecules, uncovering the formation of various superlattices,\nincluding BCC, Frank-Kasper A15, σ, Laves C14, C15, NaZn<sub>13</sub>, AlB<sub>2</sub>, and notably, the first NaCl like superlattice\nin homogeneous soft matter self-assembly. A geometric-based analysis,\ncombined with experimental results, further establishes a quantitative\nrelationship between volume asymmetry and the corresponding superlattice\nformations, thus laying a solid foundation for superlattice engineering\nwithin giant molecular systems to mimic and even beyond metal alloys.\nThe lattice parameters of various unit cells range from approximately\n5 to 20 nm. Our investigation in giant molecules could guide the advancement\nof mesoscopic, periodic soft matter materials.