Entropy-Driven Phase Separation of AIE Polysiloxanes into Porous Fibrous Films for Fluorescence Sensing

Translating the exceptional luminescent properties of AIEgens into efficient and practical sensing devices has long been a major challenge restricting their practical application. In this work, we demonstrate a novel strategy based on phase separation to fabricate stable, high-surface-area sensing films that address the fluorescence quenching typically associated with conventional nanospheres. Fluorescent polysiloxanes bearing tetraphenylphenyl (TPP) side groups were synthesized and processed into fibrous films via electrospinning. Leveraging the intrinsic incompatibility of the polymer, entropy-driven phase separation generated an “sea–island” morphology. This hierarchical structure significantly enlarged the specific surface area and facilitated analyte diffusion, thereby improving the accessibility of active sites. Molecular dynamics simulations not only predicted the formation of this architecture but also clarified the underlying entropy-driven mechanism. Overall, this work provides a solid foundation and conceptual framework for investigating how quantitative regulation of lumogenic unit density and spatial distribution governs sensing performance.