Fabrication of Au25(SG)18–ZIF‐8 Nanocomposites: A Facile Strategy to Position Au25(SG)18 Nanoclusters Inside and Outside ZIF‐8

Abstract Multifunctional composite materials are currently highly desired for sustainable energy applications. A general strategy to integrate atomically precise Au 25 (SG) 18 with ZIF‐8 (Zn(MeIm) 2 , MeIm = 2‐methylimidazole), is developed via the typical Zn‐carboxylate type of linkage. Au 25 (SG) 18 are uniformly encapsulated into a ZIF‐8 framework (Au 25 (SG) 18 @ZIF‐8) by coordination‐assisted self‐assembly. In contrast, Au 25 (SG) 18 integrated by simple impregnation is oriented along the outer surface of ZIF‐8 (Au 25 (SG) 18 /ZIF‐8). The porous structure and thermal stability of these nanocomposites are characterized by N 2 adsorption–desorption isothermal analysis and thermal gravimetric analysis. The distribution of Au 25 (SG) 18 in the two nanocomposites is confirmed by electron microscopy, and the accessibility of Au 25 (SG) 18 is evaluated by the 4‐nitrophenol reduction reaction. The as‐prepared nanocomposites retain the high porosity and thermal stability of the ZIF‐8 matrix, while also exhibiting the desired catalytic and optical properties derived from the integrated Au 25 (SG) 18 nanoclusters (NCs). Au 25 (SG) 18 @ZIF‐8 with isolated Au 25 sites is a promising heterogenous catalyst with size selectivity imparted by the ZIF‐8 matrix. The structural distinction between Au 25 (SG) 18 @ZIF‐8 and Au 25 (SG) 18 /ZIF‐8 determines their different emission features, and provides a new strategy to adjust the optical behavior of Au 25 (SG) 18 for applications in bioimaging and biotherapy.