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Metal-organic frameworks (MOFs), as a class of new inorganic-organic hybrid crystal materials, could have important applications in near-infrared (NIR) photothermal conversion. Herein, a new charge-transfer MOF (Co-MOF) with mixed ligands of H4 TTFTB and bpmNDI incorporating redox-active tetrathiafulvalene/naphthalene diimide (TTF/NDI) units into one system is reported. Due to the presence of TTF/NDI oxidative and reductive couples, stable radicals can be observed in the MOF. In addition, charge transfer from the electron donor (TTF) to