Reticular Chemistry with Art: A Case Study of Olympic Rings-Inspired Metal–Organic Frameworks

• DOI: 10.1021/jacs.2c09832
• Publication Date: 2022-11-23T16:03:17Z
• Authors: Jincheng Si; Hai-Lun Xia; Kang Zhou; Jingbai Li; Kai Xing; Jiafeng Miao; Jian Zhang; Hao Wang; Lu-Lu Qu; Xiao-Yuan Liu; Jing Li
• Keywords: Luminescence; Zirconium; Porosity; 01 natural sciences; Metal-Organic Frameworks; Density Functional Theory; 0104 chemical sciences

Herein, we demonstrate the successful utilization of reticular chemistry as an excellent designing strategy for the deliberate construction of a zirconium-tetracarboxylate metal-organic framework (MOF) inspired by the Olympic rings. HIAM-4017, with an unprecedented (4,8)-c underlying net topology termed jcs, was developed via insightful reconstruction of the rings and judicious design of a nonsymmetric organic linker. HIAM-4017 exhibits high porosity and excellent chemical and thermal stability. Furthermore, excited-state intramolecular proton transfer (ESIPT) was achieved in an isoreticular MOF, HIAM-4018, with a large Stokes shift of 155 nm as a result of introducing the hydroxyl group to the linker skeleton to induce OH···N interactions. Such interactions were analyzed thoroughly by employing the time-dependent density functional theory (TD-DFT). Because of their good thermal and chemical stability, and strong luminescence, nanosized HIAM-4017 and HIAM-4018 were fabricated and used for Cr2O72- detection. Both MOFs demonstrate excellent sensitivity and selectivity. This work represents a neat example of building structure- and property-specific MOFs guided by reticular chemistry.