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Controlling the size and morphology of metal–organic frameworks (MOF) has received increasing research interest but remains a great challenge. In this work, we demonstrate a trace-water-induced competitive coordination procedure to controllably synthesize porphyrinic MOFs including needle-shaped nanomaterials, hollow nanotubes, and nanocubes, using 5,10,15,20-tetrakis­(4-carboxyphenyl) porphyrin as organic linkers and Zr4+ as inorganic building blocks. These three MOFs exhibited shape-dependent singlet oxygen (1O2) production under 655 nm laser irradiation. The designed nanocubes were functionalized by coating a MnO2 shell, which can effectively generate 1O2 in the tumor microenvironment (TME) to improve photodynamic therapy (PDT). Moreover, they reacted with GSH, and the resulted Mn2+ions generated hydroxyl radicals (·OH) for chemodynamic therapy (CDT). Therefore, the designed MOFs@MnO2 nanoparticles were responsive to the hypoxic TME to improve the efficiency of PDT and incorporate CDT for tumor ablation.

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