Reversible modulation of interlayer stacking in 2D copper-organic frameworks for tailoring porosity and photocatalytic activity

The properties of two-dimensional covalent organic frameworks (2D COFs), including porosity, catalytic activity as well as electronic and optical properties, are greatly affected by their interlayer stacking structures. However, the precise control of their interlayer stacking mode, especially in a reversible fashion, is a long-standing and challenging pursuit. Herein, we prepare three 2D copper-organic frameworks, namely JNM-n (n = 7, 8, and 9). Interestingly, the reversible interlayer sliding between eclipsed AA stacking (i.e., JNM-7-AA and JNM-8-AA) and staggered ABC stacking (i.e., JNM-7-ABC and JNM-8-ABC) can be achieved through environmental stimulation, which endows reversible encapsulation and release of lipase. Importantly, JNM-7-AA and JNM-8-AA exhibit a broader light absorption range, higher charge-separation efficiency, and higher photocatalytic activity for sensitizing O₂ to ¹O₂ and O₂^•− than their ABC stacking isostructures. Consequently, JNM-8-AA deliver significantly enhanced photocatalytic activities for oxidative cross-coupling reactions compared to JNM-8-ABC and other reported homogeneous and heterogeneous catalysts.