College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, Guangdong 518060, China.
Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen, Guangdong 518060, China.
J Am Chem Soc. 2023 Mar 8;145(9):5191-5202. doi: 10.1021/jacs.2c11981. Epub 2023 Feb 6.
In the field of supramolecular chemistry, host-guest systems have been extensively explored to encapsulate a wide range of substrates, owing to emerging functionalities in nanoconfined space that cannot be achieved in dilute solutions. However, host-guest chemistry is still limited to encapsulation of small guests. Herein, we construct a water-soluble metallo-supramolecular hexagonal prism with a large hydrophobic cavity by anchoring multiple polyethylene glycol chains onto the building blocks. Then, assembled prisms are able to encapsulate quantum dots (QDs) with diameters of less than 5.0 nm. Furthermore, we find that the supramolecular cage around each QD strongly modifies the photophysics of the QD by universally increasing the rates of QD relaxation processes via ultrafast electron and vibrational energy transfer. Taken together, these efforts expand the scope of substrates in host-guest systems and provide a new approach to tune the optical properties of QDs.
在超分子化学领域，主体-客体体系因其在纳米受限空间中具有无法在稀溶液中实现的新兴功能而被广泛探索，以包封各种底物。然而，主体-客体化学仍然仅限于包封小分子客体。在此，我们通过将多个聚乙二醇链锚定到构筑块上来构建具有大疏水性空腔的水溶性金属超分子六方棱柱。然后，组装的棱柱能够包封直径小于 5.0nm 的量子点（QDs）。此外，我们发现每个 QD 周围的超分子笼通过超快电子和振动能量转移普遍增加 QD 弛豫过程的速率，从而强烈改变 QD 的光物理性质。总之，这些努力扩展了主体-客体体系中底物的范围，并为调节 QD 的光学性质提供了一种新方法。
