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

ABSTRACT 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.