Modulating ultralong room-temperature phosphorescence through mechanical confinement of tailored polymer/MOF hybrid...

Achieving ultra-long room temperature phosphorescence (RTP) remains a significant challenge due to the inherent trade-off between excited-state lifetime and photoluminescence quantum yield (QY). Herein, we report the synthesis of polymer/metal-organic framework (MOF) hybrids via a bottom-up approach, enabling the formation of direct covalent integration between polymer matrices and MOF structures. By systematically optimizing the incorporation of long-chain alkyl amines during the synthesis process, the resultant hybrids demonstrate green RTP performance, achieving a lifetime of 359 milliseconds (ms) at room temperature (592 ms at 77 K), and a phosphorescence QY of ∼28%, whereas no detectable phosphorescence is observed in the parent MOFs and polymer components. Notably, nanoindentation-based mechanical analysis reveals, for the first time, a clear relationship between increased matrix rigidity and enhanced RTP performance. Additionally, a detailed investigation highlights the pivotal roles of extensive intramolecular hydrogen bonding and covalent linking between the polymer and extended frameworks in stabilizing triplet states, enabling efficient RTP. The hybrid materials also demonstrate good processability, allowing the creation of flexible RTP-emissive fibers and films (lifetimes of 408 ms at RT and 613 ms at 77 K) that leverage their inherent flexibility. Furthermore, these hybrids exhibit good selectivity in detecting water over other alcohols, underscoring their potential for smart sensor applications.