While through-space conjugation (TSC) offers a powerful paradigm for constructing luminescent materials beyond planar π-systems, its deliberate integration and activation within conventional chromophoric frameworks to enhance emission remains a fundamental challenge. We address this by designing siloxane-linked fluorescent polymers (SFPs), synthesized via straightforward Heck reactions using 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and bi-, tri-, or tetra-brominated aromatic monomers. The siloxane linkage is not merely a passive spacer but actively mediates efficient TSC, endowing the polymers with remarkable dual-state emission. Notably, spirobifluorene-based polymer SFP-2 achieves photoluminescence quantum yields of up to 92.7% in solution and 23.4% in the solid state. Theoretical and spectroscopic analyses elucidate a “dynamic encapsulation” mechanism, wherein the flexible siloxane chain wraps two chromophores into a spatially proximate, non-covalently coupled assembly. This configuration suppresses intramolecular vibrational relaxation in solution, while chain entanglement in the solid state creates isolated microenvironments that inhibit aggregation-caused quenching. Leveraging this unique photophysics, the materials function as selective “turn-off” fluorescence probes for trifluralin detection under daylight and UV light, and as effective components in UV-shielding films. This work establishes a general “siloxane-activated TSC” design strategy, fundamentally underscores the active role of siloxanes in modulating optoelectronic properties, and highlights their potential in flexible electronics and sensing technologies.
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