Engineering Intraframework Energy Transfer in Metal‐Organic Frameworks for Luminescent Discrimination of Bisphenol Pollutants

ABSTRACT Luminescent sensing relies on the generation, migration, and dissipation of excited‐state energy modulated by analytes. However, the contribution of intraframework energy transfer processes to sensing performance remains insufficiently studied. Owing to the highly tunable structures and designable energy transfer pathways, metal–organic frameworks (MOFs) provide an ideal platform for dissecting detailed processes. Herein, a series of isostructural lanthanide MOFs were constructed from 2,5‐furandicarboxylic / 3,5‐pyridinedicarboxylic acid, enabling independent regulation of metal‐to‐metal and linker‐to‐linker energy transfer. Direct comparison of chemically integrated frameworks and their physical mixtures using bisphenol pollutants as probes reveals that metal‐to‐metal energy transfer dominates sensing performance, while linker‐to‐linker energy transfer contributes marginally. Mechanistic analyses indicate the impacts originate from the different energetic characteristics. Rigid lanthanide energy levels in Eu‐Tb systems create an “energy reservoir” that strongly regulate luminescence responses, whereas highly environment‐sensitive linker states in mixed‐linker systems give rise to self‐compensating energy transfer, resulting in a diminished influence. Moreover, the additional energy transfer pathways introduced by chemical integration can partially compensate for analyte‐induced excited‐state energy loss by releasing the “accumulated energy”, thereby mitigating the overall quenching effect. This work establishes a fundamental relationship between intraframework energy transfer and luminescence recognition performance, providing a general design pattern for sensing materials.