Reversible Structural Transformations of Metal–Organic Frameworks as Artificial Switchable Catalysts for Dynamic Control of Selectively Cyanation Reaction

Abstract

The synthesis of molecular-level artificial switchable catalysts, of which activity in different chemical processes can be switched by controlling different stimuli, has provided a new paradigm to perform mechanical tasks and measurable work. In this work, to obtain highly effective and regioselective artificial switchable catalysts, a hierarchical anion-pillared framework {(H₃ O)[Cu(CPCDC)(4,4'-bpy)]}_n (1; H₃ CPCDC=9-(4-carboxyphenyl)-9H-carbazole-3,6-dicarboxylic acid, 4,4'-bpy=4,4'-bipyridine), including free [H₃ O]⁺ ions as guest molecules, was constructed. Upon dissolve-exchange-crystallization behavior, fascinating reversible structural transformations proceeded between anion framework 1 and neutral 2D stair-stepping framework {[Cu(CPCDC)(4,4'-bpe)]}_n (2; 4,4'-bpe=4,4'-vinylenedipyridine). Moreover, frameworks 1 and 2 can act as heterogeneous artificial switchable catalysts to selectively promote the direct cyanation reaction of terminal alkynes and azobisisobutyronitrile. The results indicated that 1 and 2 exhibited excellent selectivity to generate vinyl isobutyronitrile skeletons or propiolonitrile frameworks, respectively, as unique products. Furthermore, indicating paper, GC-MS, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis demonstrated that the reversible structural transformations endowed 1 and 2 with well-defined platforms to stabilize the isobutyronitrile and CN sources through the different catalytic pathways.