Supramolecular Coordination Platforms for Smart Theranostics: Leveraging the Dynamic Molecular Networks of Metal–Polyphenol Assemblies

ABSTRACT Metal–polyphenol networks (MPNs), as supramolecular functional materials formed through coordination‐driven self‐assembly of polyphenol ligands and metal ions (Fe 2+ , Cu 2+ , etc.), have demonstrated broad application prospects in the biomedical field due to their structural designability, excellent biocompatibility, and stimulus‐responsive degradation properties. MPNs allow for precise control over coordination kinetics, stability, and functionality through diverse combinations of polyphenols and metal ions. Various assembly methods, including the template method, nanoprecipitation, layer‐by‐layer self‐assembly, and one‐pot synthesis, have successfully led to the construction of diverse structures such as films, nanoparticles, hollow capsules, hydrogels, and metal–organic frameworks. By adjusting the metal‐to‐polyphenol ratio, pH, reaction time, and introducing functional molecules, the size, surface charge, mechanical properties, and dissociation behavior of MPNs can be effectively controlled to meet the demands of various biomedical applications. Leveraging the synergistic interaction between paramagnetic or fluorescent metal ions and polyphenol structures, MPNs are widely used in the design of probes for magnetic resonance imaging, fluorescence imaging, photoacoustic imaging, and multimodal imaging, enabling precise localization and real‐time monitoring of pathological sites. MPNs not only serve as highly efficient drug delivery carriers, enabling targeted release in response to the micro acidic or high reactive oxygen species environments of tumors, but also play a critical role in synergistic disease therapy through the enzymatic‐like catalytic activity, photothermal conversion capabilities, and radiosensitizing effects of metal ions. In this review, we summarize the advances of MPNs as a highly versatile and functionally integrated supramolecular assembly platform, and discuss their pivotal role in steering biomedical materials away from single‐function designs and toward intelligent, unified diagnostic and therapeutic solutions.