Unconventional Supramolecular Alloy Phases Constructed By Spherical Motifs In Soft Matters

Complex superlattices formed by spherical motifs in soft matter have potential application in many aspects,and their properties mainly depend on the lattice dimension and packing structures.A series of discotic molecules with similar chemical structures were designed and synthesized.All of the assembly methods are driven by hydrogen bonding interaction,and the differences between their packing structures are systematically studied.As a result,a relationship between molecular structures and spherical motif sizes is established.Furthermore,spherical motifs formed by two molecules were found in blend of two molecules with the same core,and the hexagonal close packing（HCP）structure constructed in the blend indicated the identity of spherical motifs,which appeared to be a novel method to adjust the size of these spherical motifs conventionally and slightly by varying the content of two molecules.A creative self-sorting assembly strategy was utilized to construct unconventional superlattices based on spherical motifs in soft matter binary blends.Two types of giant shape amphiphiles with different cores self-sort to form discrete spherical motifs,and the spherical motifs with various sizes further packed into alloy-originated superlattices.Three unconventional phases are found in the binary blends,including Mg Zn₂,Na Zn₁₃,and Ca Cu₅phases.It’s the first observation of Ca Cu₅ phase in soft matter.Isoperimetric quotient was introduced to explain the packing structures in binary blends,and based on the calculation,the formation of other superlattices with higher volume asymmetry were predicted.Isoperimetric quotient was further used to measure the stability of several Frank-Kasper phases constructed by spherical motifs with various volumes,and the spherical motif number was also considered to be a key factor at the first time.Based on the calculation,a phase diagram in binary-sphere system was established,which coincided with the packing structures in experimental results.Notably,M phase,μphase and pσphase were predicted to form in ternary-sphere systems with specific spherical motif number ratio and volume ratio.The limitation of isoperimetric quotient was also discussed,which could be a guidance towards Frank-Kasper phases with low spherical symmetry,anda new field of superlattice engineering is created experimentally and theoretically.