Photoswitchable Catalysis by a Self-Assembled Molecular Cage

Photoswitchable Catalysis by a Self-Assembled Molecular Cage

July 25, 2024 | Ray G. DiNardi, Samina Rasheed, Simona S. Capomolla, Man Him Chak, Isis A. Middleton, Lauren K. Macreadie, Jake P. Violi, William A. Donald, Paul J. Lusby, Jonathon E. Beves
The paper presents a novel approach to photoswitchable catalysis within a self-assembled molecular cage. The authors developed a heteroleptic [Pd2L2L2]4+ coordination cage containing a photoswitchable azobenzene-derived ligand, which catalyzes the Michael addition reaction between methyl vinyl ketone and benzoyl nitromethane. The cage can be reversibly disassembled and reassembled using 530 nm and 405 nm light, respectively, allowing the catalytic activity to be switched on and off at will. The homoleptic cages, which lack the photoswitchable ligand, are catalytically inactive. The study highlights the potential of using light-responsive molecular cages to control chemical reactions, providing a new method for directing chemical processes with high spatio-temporal resolution. The mechanism of catalysis relies on electrostatic interactions within the cavity, which are facilitated by the shape complementarity of the heteroleptic cage. The system demonstrates excellent reversibility and can be subjected to multiple cycles of photoswitching without affecting catalytic performance.The paper presents a novel approach to photoswitchable catalysis within a self-assembled molecular cage. The authors developed a heteroleptic [Pd2L2L2]4+ coordination cage containing a photoswitchable azobenzene-derived ligand, which catalyzes the Michael addition reaction between methyl vinyl ketone and benzoyl nitromethane. The cage can be reversibly disassembled and reassembled using 530 nm and 405 nm light, respectively, allowing the catalytic activity to be switched on and off at will. The homoleptic cages, which lack the photoswitchable ligand, are catalytically inactive. The study highlights the potential of using light-responsive molecular cages to control chemical reactions, providing a new method for directing chemical processes with high spatio-temporal resolution. The mechanism of catalysis relies on electrostatic interactions within the cavity, which are facilitated by the shape complementarity of the heteroleptic cage. The system demonstrates excellent reversibility and can be subjected to multiple cycles of photoswitching without affecting catalytic performance.
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