Precise control over the photocatalytic selectivity by single atoms is ubiquitous in natural systems but remains a formidable challenge for artificial photocatalysts. Here, we present a series of porphyrin-based metallacages with nearly identical architectures that differ only in the central metal atoms (Co, Ni, Cu, and Zn) of the porphyrin ligands. The distinctd-orbital electron distribution of these metal centers governs ligand-to-metal charge transfer, resulting in divergent reactive oxygen species (ROS) generation pathways. The Co–porphyrin cage promotes electron transfer to produce superoxide anion (O2•−), whereas the Zn–porphyrin cage favors energy transfer to generate singlet oxygen (1O2); Ni- and Cu-porphyrin cages exhibit dual behavior. These variations lead to distinct oxidation selectivity of α-terpinene, yielding eitherp-cymene (via O2•−) or ascaridole (via1O2). Moreover, secondary coordination between the porphyrin metals and poly(4-vinylpyridine) affords robust supramolecular networks for heterogeneous catalysis with enhanced stability and recyclability. This study establishes single-atom modulation within metallacage frameworks as an effective strategy to control ROS generation and photocatalytic selectivity, paving the way toward the practical applications of metallacage-based photocatalytic systems.

Single‐Atom‐Modulated Reactive Oxygen Species Generation and Network Crosslinking in Porphyrin‐Based Metallacages for Selective Photocatalysis - Zhang - 2026 - Angewandte Chemie International Edition - Wiley Online Library