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Photoswitchable coordination cages

Nature Chemistry volume 16, pages 13–21 (2024)Cite this article

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Abstract

Stimuli-responsive behaviour is key to the design of smart materials, surfaces, nano-systems and effector molecules, allowing their application as switchable catalysts, molecular transporters, bioimaging probes or caged drugs. Supramolecular chemistry has embraced the widespread integration of photoswitches because of their precise spatiotemporal addressability and waste-free nature. In the vibrant area of discrete metal-mediated self-assembly, however, photoswitches are still rarely employed. Only recently has it been shown that embedding photoswitches into the organic backbones of coordination cages enables control of their host and material properties and thus unlocks the hitherto unexploited dynamic adaptivity of such systems. Here we discuss four cases where triggering ligand-integrated photoswitches leads to (1) control over disassembly/reassembly, (2) bi-stable switching between defined states, (3) interplay with thermal processes in metastable systems and (4) light-fuelled dissipative self-assembly. We highlight first clues concerning the relationship between fundamental photophysics and dynamic assembly equilibria and propose directions for future development.

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Fig. 1: Introducing photoswitchable behaviour into metal-mediated assemblies.
Fig. 2: Light-triggered, reversible disassembly and reassembly of azobenzene-based metallosupramolecular structures.
Fig. 3: Bi-stable photoswitchable [Pd2L4] assemblies.
Fig. 4: Light-triggered metastable assemblies.

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Acknowledgements

This work was funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under the GRK2376 ‘Confinement Controlled Chemistry’ project no. 331085229, under Germany’s Excellence Strategy EXC 2033 “RESOLV”, project no. 390677874, and grant no. CL 489/2-2.

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  1. Department of Chemistry and Chemical Biology, TU Dortmund University, Dortmund, Germany

    Elie Benchimol, Jacopo Tessarolo & Guido H. Clever

  2. Department of Chemistry, Chonnam National University, Gwangju, Republic of Korea

    Jacopo Tessarolo

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Benchimol, E., Tessarolo, J. & Clever, G.H. Photoswitchable coordination cages. Nat. Chem. 16, 13–21 (2024). https://doi.org/10.1038/s41557-023-01387-8

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