Benchimol Elie, Tessarolo Jacopo, Clever Guido H
Department of Chemistry and Chemical Biology, TU Dortmund University, Dortmund, Germany.
Department of Chemistry, Chonnam National University, Gwangju, Republic of Korea.
Nat Chem. 2024 Jan;16(1):13-21. doi: 10.1038/s41557-023-01387-8. Epub 2024 Jan 5.
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.
刺激响应行为是智能材料、表面、纳米系统和效应分子设计的关键，使其能够用作可切换催化剂、分子转运体、生物成像探针或笼形药物。超分子化学因其精确的时空可寻址性和无废物性质，广泛采用了光开关。然而，在离散金属介导的自组装这个活跃领域，光开关的应用仍然很少。直到最近才表明，将光开关嵌入配位笼的有机骨架中，可以控制其主体和材料特性，从而开启此类系统迄今未被开发的动态适应性。在这里，我们讨论了四种情况，即触发配体整合的光开关会导致：（1）对拆卸/重新组装的控制；（2）在特定状态之间的双稳态切换；（3）与亚稳态系统中的热过程相互作用；（4）光驱动的耗散自组装。我们强调了关于基本光物理与动态组装平衡之间关系的初步线索，并提出了未来发展的方向。
