Sequential module coordination-driven programmable function switch of metal-molecule nanoframeworks for cancer theranostics

Coordination chemistry-driven self-assembly of molecular motifs is an emerging powerful means to construct functional materials for biomedical fields. However, how to readily achieve functional manipulation by modulating intermolecular binding behaviors of diverse molecular modules remains challenging. Inspired by natural molecule interaction events, here we report a straightforward methodology to fabricate metal-molecule nanoframeworks with programmable functions, by simply integrating a function-switching module in well-defined nonfunctional/single-function frameworks, mediated by a sequential module coordination mechanism. Such concept is successfully demonstrated by manipulating the coordination between classic function-silent MIL-100(Fe) and catechol molecules. Without the need of complicated ligand design and synthesis, this strategy endows frameworks with multiple functionalities to execute a “1 + 1 + 1 > 3” synergistic theranostic effect, including photothermal conversion, photoacoustic effect, prominent T1 relaxation, and enhanced Fenton catalysis for cancer imaging and tumor depletion. This work offers a way to create advanced frameworks and promote continually expanding interest for the interdisciplinary discipline of coordination chemistry and biomedicine.