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

Spherical surfactant micelles, widely used as templates for synthesizing porous inorganic materials, suffer from undeterminable atomic-level structures. Developing structurally precise spherical micelle-like architectures is therefore highly beneficial for understanding template syntheses yet remains challenging. Here, we demonstrate a series of micelle-like π-stacked architectures self-assembled from tripodal synthons ([ML(SO 4 )], [ML(SCN)] +, or [H 3 L(HPO 4 )] +, where M = Co 2+ or Zn 2+ and L = tris(2-benzimidazolylmethyl)amine). These structures form through anion-coordination-regulated π–π stacking. While a honeycomb architecture of oppositely aligned neutral [CoL(SO 4 )] forms without the directing of anions, various cationic micelle-like π-stacked architectures of [ML(SCN)] + and [H 3 L(HPO 4 )] + 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.