Nonequilibrium Navigation of a Rugged Energy Landscape Enables the Formation of Face-On Single-Domain Dodecagonal Quasicrystals

Abstract Metastable intermediates play an important role in directing structural evolution across complex energy landscapes. Here, we establish the dodecagonal quasicrystal (DDQC) as a tunable metastable kinetic junction in a single-component carboxyl-functionalized dendritic assembly. Time-resolved small-angle X-ray scattering (SAXS) reveals that this DDQC junction bifurcates into distinct Frank–Kasper (FK) phases through competing kinetic pathways: a deformation-dominated route to the A15 phase at lower temperatures or a mass-exchange-mediated transformation to the thermodynamically favored σ phase at higher temperatures. By introducing amine-mediated salt bridges to rigidify the micellar cores, we selectively suppress the deformation-driven A15 pathway while preserving access to the σ phase, thereby programming the bifurcation behavior of the DDQC junction. Leveraging this core engineering, a vapor-induced self-assembly (VISA) strategy was further developed to enable a nonequilibrium σ-to-DDQC transition. The high nucleation barrier inherent to this nonequilibrium pathway creates a nucleation-controlled regime that suppresses spontaneous polydomain formation, enabling the growth of macroscopically aligned, face-on single-domain DDQC with persistent 12-fold symmetry over millimeter length scales. These findings demonstrate that micellar core engineering provides a powerful platform for navigating rugged energy landscapes, transforming metastability from an uncontrolled kinetic trap into a programmable element for deterministic pathway selection and long-range quasiperiodic order in soft matter.