TI Sequentially Regulating the Structural Transformation of Copper Metal-Organic Frameworks (Cu-MOFs) for Controlling Site-Selective Reaction
AB Regulating atomically precise sites in catalysts to achieve site-selective reactions is remarkable but challenging. In this work, a convenient and facile solid-gas/ liquid reaction strategy was used to construct controllable active sites in metal-organic frameworks (MOFs) to guide an orientation site-selective reaction. A flexible Cu-I-MOF-1 with dynamics originating from an anionic and tailorable framework could undergo a reversible structural transformation to engineer a topologically equivalent mixed-valent (CuCuII)-Cu-I-MOF-2 via a solid-gas/liquid oxidation/reduction process. More importantly, Cu-I-MOF-1 and (CuCuII)-Cu-I-MOF-2 could further execute the solid-gas/liquid reaction under ammonia vapor/solution to generate Cu-II-MOF-3. Furthermore, the transformation from Cu-I-MOF-1 to (CuCuII)-Cu-I-MOF-2 and Cu-II-MOF-3 served as controllable catalysts to facilitate site-selective reactions to realize direct C-N bond arylations. The results demonstrated that Cu-I-MOF-1 and Cu-II-MOF-3 possessed well-defined platforms with uniformly and accurately active sites to attain a "turn-on/off " process via different reaction routes, providing the desired site-selective ring-opening products.
