Photoreaction Boosting Phosphorescence Cascade Energy Transfer Based on Cucurbit[8]Uril Biaxial Polypseudorotaxane

• Published in: Advanced optical materials 2023-04, Vol.11 (7), p.n/a
• Main Authors: Xing, Wen‐Wen, Wang, Hui‐Juan, Liu, Zhixue, Yu, Zhen‐Hai, Zhang, Heng‐Yi, Liu, Yu
• Format: Article
• Language: English
• Subjects: cascade energy transfer; near‐infrared cell imaging; photodimerization; room temperature phosphorescence
• ISSN: 2195-1071; 2195-1071
• DOI: 10.1002/adom.202202588

Cascade energy capturers based on supramolecular assembly have recently generated great research interest in the field of luminescent materials. Herein is reported a cucurbit[8]uril (CB[8])‐encapsulated coumarin‐bridged phenylpyridinium salt (G) to form biaxial polypseudorotaxane (G⊂CB[8]), which not only induces the phosphorescence of the guest G, but also activates the photodimerization of coumarin functional group in the CB[8] cavity (G‐dimer⊂CB[8]) to further boost its phosphorescence emission, extending the phosphorescence lifetime from 271.3 to 430.3 µs and the quantum yield from 5.1% to 25.7% in aqueous solution. After co‐assembly with amphiphilic calixarene (SC4AD), the supramolecular biaxial polypseudorotaxane G‐dimer⊂CB[8] is changed to the nanoparticle. Compared with the alone G‐dimer⊂CB[8], the phosphorescence intensity of G‐dimer⊂CB[8]@SC4AD is significantly enhanced with the phosphorescence lifetime extending to 2.11 ms. Subsequently, by doping commercial dye rhodamine B (RhB) in the G‐dimer⊂CB[8]@SC4AD assembly, an ultrahighly efficient phosphorescence‐harvesting energy transfer process occurs with an energy transfer efficiency (ΦET) of 72.3% and an antenna effect of 396.8. Furthermore, the cascaded room temperature phosphorescence harvesting system is constructed via introducing the secondary near‐infrared (NIR) acceptors Nile blue or Cy5 in the G‐dimer⊂CB[8]@SC4AD:RhB system, which possesses a good biocompatibility and is successfully applied to NIR delayed fluorescence targeted imaging in HeLa cell. A long‐life, high‐efficiency phosphorescent cascade light capture system based on biaxial polypseudorotaxane, which is enhanced by photoreaction, is constructed to obtain ultrahigh antenna effect and is applied to delayed fluorescence cell imaging.