A 3D Terbium-Porphyrin Framework for Visible-Light-Driven Singlet Oxygen Generation and Photocatalytic Oxidation

Elucidating the structural evolution of secondary building units (SBUs) in lanthanide-porphyrin frameworks (Ln-PMOFs) remains a compelling challenge in targeted crystal engineering. Herein, a novel 3D framework, QPF-13, featuring unique intermediate-nuclearity Tb 3 and Tb 4 clusters, was synthesized from Tb (III) and tetrakis(3-carboxyphenyl)porphyrin. Significantly, QPF-13 bridges the structural gap between previously established low-nuclearity (Ln 2 ) and high-nuclearity (Ln 7 /Ln 9 ) extremes, successfully completing the SBU evolutionary landscape within this systematic series. Furthermore, the rigid spatial confinement of the porphyrin macrocycles effectively suppresses self-quenching, enabling robust visible-light-driven singlet oxygen generation. Consequently, QPF-13 demonstrates excellent photocatalytic performance in the selective oxidation of 1,5-dihydroxynaphthalene. This work provides deep crystallographic insights into Ln-coordination assembly and establishes a rational structural library for designing advanced photooxidation catalysts.