Abstract Regulating the generation of reactive oxygen species (ROS) plays a crucial role in the selectivity and activity of photocatalytic oxidation, but the current regulation strategies have been limited to unit variation. Herein, two atomically precise porphyrinic silver cluster assembled materials are elaborately designed and constructed via the solvent‐triggered connectivity engineering. The two Ag cluster‐based frameworks, Cl@Ag 16 (S t Bu) 8 (CF 3 COO) 7 (TPyP)(DMF) n ( 2D‐Ag 16 ‐TPyP ) and Cl@Ag 16 (S t Bu) 8 (CF 3 COO) 6 (MeO)(TPyP)(H 2 O) n ( 3D‐Ag 16 ‐TPyP ), feature different dimensionality and topological structures, which can be attributed to flexible connectivity offered by labile ligands. Remarkably, 2D‐Ag 16 ‐TPyP facilitates the coexistence of 1 O 2 and O 2 •− under photoexcitation. By contrast, 3D‐Ag 16 ‐TPyP exhibited a superior performance in activating O 2 to form 1 O 2 compared to its 2D counterpart. The photoelectro‐chemical study conjugated with density‐functional theory (DFT) calculations revealed that the distinct connection modes can not only cause differences in O 2 adsorption affinity, but also directly influence HOMO‐LUMO distribution, which can affect electron/energy transfer efficiency and O 2 •− / 1 O 2 generation. Furthermore, the manipulation of ROS generation pathways of 2D‐Ag 16 ‐TPyP and 3D‐Ag 16 ‐TPyP successively leads to distinct performance in two specific photocatalytic oxidations. This study demonstrates a highly efficient strategy that utilizes synergistic modulation of O 2 adsorption capability and molecular orbital distribution to regulate the generation of ROS via connectivity engineering.
Yang et al. (Thu,) studied this question.