Dual-Functional Photocatalysis Enabled by a Benzo(triazole-thiadiazole)-Based Metal–Organic Framework

The rational design of photocatalytically active metal–organic frameworks is essential for advancing sustainable and selective synthesis. Herein, we report a zirconium-based MOF (Zr-TB-fcu-MOF) assembled from a π-extended, nitrogen-rich benzo(triazole-thiadiazole) linker. The incorporation of a donor–acceptor–donor (D–A–D) architecture within the fcu-type framework induces pronounced intraframework electronic polarization, facilitating efficient photoinduced charge separation under visible-light irradiation. Structural and spectroscopic analyses reveal that the crystalline network exhibits high porosity, suitable band alignment, and good chemical stability. These combined characteristics enable Zr-TB-fcu-MOF to function as a robust and recyclable heterogeneous photocatalyst, promoting the atom-economical synthesis of nitrogen-containing compounds under mild additive-free conditions. The catalyst mediates the formation of symmetrical (up to 85% yield) and unsymmetrical (up to 40% yield) thiadiazoles as well as imines (up to 99% yield), showing good tolerance toward the functional groups present in the tested substrates and maintaining catalytic activity over multiple cycles. This work demonstrates a structure-guided approach for engineering MOF-based photocatalysts with tunable electronic structures for visible-light-driven organic transformations.