Scalable Aqueous Polymerization Via Nanoconfinement Effect Generating Two‐Dimensional Polymers With Excitation‐Dependent Clusteroluminescence

Organic two-dimensional polymers (O2DPs) with molecular-scale thickness are at the forefront of material research due to their attractive properties. However, current mainstream synthesis methods for O2DP are generally inefficient due to the requirement of crystalline monomers or rely on specific interfaces, which severely limited their practical applications. Herein, we report facile and efficient synthesis of O2DP in aqueous solution at a high concentration of 50 mg/mL. In this approach, amphiphilic monomers first self-assemble into 2D bilayers through the synergistic action of noncovalent interactions such as hydrogen bonding, π-π stacking, and electrostatic repulsion, and subsequent radical polymerization within these sheets produces O2DP with a 2D covalent network. Notably, the hydrogen-bonding network promotes electron delocalization and through-space conjugation, giving rise to clusterization-triggered emission (CTE) with excitation-dependent color tunability. Compared with its supramolecular precursors, the O2DP exhibits significantly enhanced clusteroluminescence even in dilute solution due to rigid covalent crosslinked structure. These 2D materials can serve as excellent coatings or nanofillers providing different substrates with color-tunable luminescence and room-temperature phosphorescence (RTP) while providing superior performance in stability, emission intensity, and mechanical reinforcement. This work provides a robust and scalable strategy for fabricating functional O2DPs, promising for applications in optics, smart coatings, and high-performance composites.