Porphyrin-Based Multicomponent Metallacage: Host-Guest Complexation toward Photooxidation-Triggered Reversible Encapsulation and Release

Zeyuan Zhang; Lingzhi Ma; Fang Fang; Yali Hou; Chenjie Lu; Chaoqun Mu; Yafei Zhang; Haifei Liu; Ke Gao; Ming Wang; Zixi Zhang; Xiaopeng Li; Mingming Zhang

doi:10.1021/jacsau.2c00245

Porphyrin-Based Multicomponent Metallacage: Host-Guest Complexation toward Photooxidation-Triggered Reversible Encapsulation and Release

JACS Au. 2022 Jun 1;2(6):1479-1487. doi: 10.1021/jacsau.2c00245. eCollection 2022 Jun 27.

Authors

Zeyuan Zhang¹, Lingzhi Ma¹, Fang Fang², Yali Hou¹, Chenjie Lu³, Chaoqun Mu¹, Yafei Zhang¹, Haifei Liu¹, Ke Gao¹, Ming Wang⁴, Zixi Zhang⁵, Xiaopeng Li⁶, Mingming Zhang¹

Affiliations

¹ 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.
² Instrumental Analysis Center of Shenzhen University, Shenzhen 518055, P. R. China.
³ Key Laboratory of Adsorption and Separation Materials and Technologies of Zhejiang Province, Zhejiang University, Hangzhou 310027, P. R. China.
⁴ State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. China.
⁵ Department of Dermatology, The First Affiliated Hospital of Xi'an Jiaotong University, Xi'an 710061, P. R. China.
⁶ College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518055, P. R. China.

Abstract

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 × 10⁷ M^-1 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.