Zhang Zeyuan, Ma Lingzhi, Fang Fang, Hou Yali, Lu Chenjie, Mu Chaoqun, Zhang Yafei, Liu Haifei, Gao Ke, Wang Ming, Zhang Zixi, Li Xiaopeng, Zhang Mingming
State Key Laboratory for Mechanical Behavior of Materials, Shaanxi International Research Center for Soft Matter, School of Materials Science and Engineering, Xi'an Jiaotong University, Xi'an 710049, P. R. China.
Instrumental Analysis Center of Shenzhen University, Shenzhen 518055, P. R. China.
JACS Au. 2022 Jun 1;2(6):1479-1487. doi: 10.1021/jacsau.2c00245. eCollection 2022 Jun 27.
The development of supramolecular hosts with effective host-guest properties is crucial for their applications. Herein, we report the preparation of a porphyrin-based metallacage, which serves as a host for a series of polycyclic aromatic hydrocarbons (PAHs). The association constant between the metallacage and coronene reaches 2.37 × 10 M in acetonitrile/chloroform (ν/ν = 9/1), which is among the highest values in metallacage-based host-guest complexes. Moreover, the metallacage exhibits good singlet oxygen generation capacity, which can be further used to oxidize encapsulated anthracene derivatives into anthracene endoperoxides, leading to the release of guests. By employing 10-phenyl-9-(2-phenylethynyl)anthracene whose endoperoxide can be converted back by heating as the guest, a reversible controlled release system is constructed. This study not only gives a type of porphyrin-based metallacage that shows desired host-guest interactions with PAHs but also offers a photooxidation-responsive host-guest recognition motif, which will guide future design and applications of metallacages for stimuli-responsive materials.
具有有效主客体性质的超分子主体的开发对其应用至关重要。在此，我们报道了一种基于卟啉的金属笼的制备，该金属笼作为一系列多环芳烃（PAHs）的主体。在乙腈/氯仿（ν/ν = 9/1）中，金属笼与蔻的缔合常数达到2.37×10 M，这是基于金属笼的主客体配合物中的最高值之一。此外，该金属笼表现出良好的单线态氧生成能力，可进一步用于将包封的蒽衍生物氧化为蒽内过氧化物，从而导致客体释放。通过使用其过氧化物可通过加热转化回原状的10-苯基-9-(2-苯乙炔基)蒽作为客体，构建了一个可逆控释系统。这项研究不仅给出了一种与PAHs表现出理想主客体相互作用的基于卟啉的金属笼，还提供了一种光氧化响应型主客体识别基序，这将指导金属笼在刺激响应材料方面的未来设计和应用。
