A delicate balance of noncovalent interactions directs the hierarchical self-assembly of molecular amphiphiles into spherical micelles that pack into three-dimensional periodic arrays, which mimic intermetallic crystals. Herein, we report the discovery that adding water to a mixture of an ionic surfactant and n-decane induces aperiodic ordering of oil-swollen spherical micelles into previously unrecognized, aqueous lyotropic dodecagonal quasicrystals (DDQCs), which exhibit local 12-fold rotational symmetry and no long-range translational order. The emergence of these DDQCs at the nexus of dynamically arrested micellar glasses and a periodic Frank–Kasper (FK) σ phase approximant sensitively depends on the mixing order of molecular constituents in the assembly process and on sample thermal history. Addition of n-decane to mixtures of surfactant and water instead leads only to periodic FK A15 and σ approximants with no evidence for aperiodic order, while extended ambient temperature annealing of the DDQC also reveals its transformation into a σ phase. Thus, these lyotropic DDQCs are long-lived metastable morphologies, which nucleate and grow from a stochastic distribution of micelle sizes formed by abrupt segregation of varied amounts of oil into surfactant micelles on hydration. These findings indicate that molecular building block complexity is not a prerequisite for the formation of aperiodic supramolecular order, while also establishing the generic nature of quasicrystalline states across metal alloys and self-assembled micellar materials.

非共价相互作用的微妙平衡将分子两亲物的分层自组装引导成球形胶束，该胶束包装成模拟金属间化合物晶体的三维周期性阵列。在这里，我们报告了在离子表面活性剂和正癸烷的混合物中加入水会诱导油溶胀球形胶束非周期性排列成以前无法识别的水性溶致十二边形准晶体 (DDQC) 的发现，其表现出局部 12 倍旋转对称性和没有长程平移顺序。这些 DDQC 在动态阻滞胶束玻璃和周期性 Frank-Kasper (FK) σ 相近似处的出现敏感地取决于组装过程中分子成分的混合顺序和样品热历史。外加的正癸烷转化为表面活性剂和水的混合物只会导致周期性 FK A15 和 σ 近似值，没有证据表明非周期性顺序，而 DDQC 的扩展环境温度退火也揭示了它向 σ 相的转变。因此，这些易溶 DDQC 是长寿命的亚稳态形态，其成核并从胶束尺寸的随机分布中生长，这些胶束尺寸是由不同量的油在水合时突然分离成表面活性剂胶束而形成的。这些发现表明，分子结构单元的复杂性不是形成非周期性超分子有序的先决条件，同时也确立了金属合金和自组装胶束材料中准晶态的一般性质。