Photoswitchable Catalysis by a Self-Assembled Molecular Cage

Photoswitchable Catalysis by a Self-Assembled Molecular Cage

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
A photoswitchable molecular cage based on a heteroleptic [Pd₂L₂L₂′]⁴⁺ coordination complex catalyzes the Michael addition reaction between methyl vinyl ketone and benzoyl nitromethane. The cage can be reversibly disassembled and reassembled using 530 and 405 nm light, enabling catalysis to be switched on and off. The heteroleptic cage contains a photoswitchable azobenzene-derived ligand, which allows for controlled catalytic activity. In contrast, homoleptic cages are catalytically inactive. The cage's ability to switch between states is attributed to its unique structure, which facilitates guest binding and catalytic activity. The study demonstrates the first example of photoswitchable catalysis within a self-assembled molecular cage, with the mechanism relying on electrostatic interactions within the cavity. The catalytic activity can be controlled using visible light, offering a new method for directing chemical reactions. The system can undergo multiple cycles of photoswitching without affecting catalytic performance. The results highlight the potential of photoswitchable molecular cages for controlling chemical reactivity through light.A photoswitchable molecular cage based on a heteroleptic [Pd₂L₂L₂′]⁴⁺ coordination complex catalyzes the Michael addition reaction between methyl vinyl ketone and benzoyl nitromethane. The cage can be reversibly disassembled and reassembled using 530 and 405 nm light, enabling catalysis to be switched on and off. The heteroleptic cage contains a photoswitchable azobenzene-derived ligand, which allows for controlled catalytic activity. In contrast, homoleptic cages are catalytically inactive. The cage's ability to switch between states is attributed to its unique structure, which facilitates guest binding and catalytic activity. The study demonstrates the first example of photoswitchable catalysis within a self-assembled molecular cage, with the mechanism relying on electrostatic interactions within the cavity. The catalytic activity can be controlled using visible light, offering a new method for directing chemical reactions. The system can undergo multiple cycles of photoswitching without affecting catalytic performance. The results highlight the potential of photoswitchable molecular cages for controlling chemical reactivity through light.
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