Regulating π-Stacked Micelle-Like Assembly via Anion Coordination to Achieve Frank–Kasper C15 Phases

are successfully constructed via anion coordination-regulated π-π stacking. Within these assemblies, the π-stacked tripodal synthons and the H-bonded anion networks mutually template each other, reminiscent of how surfactant micelles template porous inorganic materials. Remarkably, this approach yields two new Frank-Kasper (FK) C15 phases, representing the first FK C15 complexes formed by small-molecule assembly. These results establish a universal strategy leveraging the interplay between π-π stacking and anion coordination to access complex supramolecular FK structures, potentially enabling new synthetic approaches for porous inorganic materials such as zeolites and porous silicon.