Colomban Cédric, Fuertes-Espinosa Carles, Goeb Sébastien, Sallé Marc, Costas Miquel, Blancafort Lluís, Ribas Xavi
Institut de Química Computatcional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, Girona, E17003, Catalonia, Spain.
Laboratoire MOLTECH-Anjou, Université d'Angers, CNRS UMR 6200, 2 bd Lavoisier, 49045, Angers Cedex, France.
Chemistry. 2018 Mar 20;24(17):4371-4381. doi: 10.1002/chem.201705531. Epub 2018 Feb 21.
We demonstrate the benefits of using cofacial Zn-porphyrins as structural synthons in coordination-driven self-assembled prisms to produce cage-like singlet oxygen ( O ) photosensitizers with tunable properties. In particular, we describe the photosensitizing and emission properties of palladium- and copper-based supramolecular capsules, and demonstrate that the nature of the bridging metal nodes in these discrete self-assembled prisms strongly influences O generation at the Zn-porphyrin centers. The Pd -based prism is a particularly robust photosensitizer, whereas the Cu self-assembled prism is a dormant photosensitizer that could be switched to a ON state upon disassembly of the suprastructure. Furthermore, the well-defined cavity within the prisms allowed encapsulation of pyridine-based ligands and fullerene derivatives, which led to a remarkable guest tuning of the O production.
我们展示了在配位驱动的自组装棱镜中使用共面锌卟啉作为结构合成子以制备具有可调谐性质的笼状单线态氧（O）光敏剂的益处。特别地，我们描述了钯基和铜基超分子胶囊的光敏和发光性质，并证明这些离散自组装棱镜中桥连金属节点的性质强烈影响锌卟啉中心处单线态氧的产生。钯基棱镜是一种特别稳定的光敏剂，而铜自组装棱镜是一种休眠光敏剂，在超结构解体时可转变为开启状态。此外，棱镜内明确界定的空腔允许封装吡啶基配体和富勒烯衍生物，这导致单线态氧产生的显著客体调控。
