Nonequilibrium Navigation of a Rugged Energy Landscape Enables the Formation of Face-On Single-Domain Dodecagonal Quasicrystals.
- 1Department of Chemistry, National Taiwan University, No. 1, Sec. 4, Roosevelt Rd, Taipei10617, Taiwan.
- 2National Synchrotron Radiation Research Center , 101 Hsin-Ann Road, Hsinchu30076, Taiwan.
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.
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BibTeX
@article{egashira2026nonequilibrium,
title = {{Nonequilibrium Navigation of a Rugged Energy Landscape Enables the Formation of Face-On Single-Domain Dodecagonal Quasicrystals.}},
author = {Mayumi Egashira and Jing-Wei Chen and Mao-Yan Wang and Chun-Jen Su and Yi-Qi Yeh and Wei-Tsung Chuang and Chien-Lung Wang},
journal = {Journal of the American Chemical Society},
year = {2026},
month = sep,
doi = {10.1021/jacs.6c09814},
url = {https://europepmc.org/article/MED/42954511},
note = {CC BY},
}
RIS
TY - JOUR
TI - Nonequilibrium Navigation of a Rugged Energy Landscape Enables the Formation of Face-On Single-Domain Dodecagonal Quasicrystals.
AU - Mayumi Egashira
AU - Jing-Wei Chen
AU - Mao-Yan Wang
AU - Chun-Jen Su
AU - Yi-Qi Yeh
AU - Wei-Tsung Chuang
AU - Chien-Lung Wang
PY - 2026
DA - 2026/09/30
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c09814
UR - https://europepmc.org/article/MED/42954511
AB - 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.
SN - 0002-7863
SN - 1520-5126
ER -