Rapid Generation of Hierarchically Porous Metal–Organic Frameworks through Laser Photolysis. Issue 28 (11th May 2020)

• Record Type: Journal Article
• Authors: Wang, Kun‐Yu; Feng, Liang; Yan, Tian‐Hao; Wu, Shengxiang; Joseph, Elizabeth A.; Zhou, Hong‐Cai
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 28(2020)
• Page Start: 11349
• Page End: 11354
• Publication Date: 2020-05-11
• Subjects: hierarchical pores -- linker photolysis -- metal–organic frameworks; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202003636
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Hierarchically porous metal–organic frameworks (HP‐MOFs) facilitate mass transfer due to mesoporosity while preserving the advantage of microporosity. This unique feature endows HP‐MOFs with remarkable application potential in multiple fields. Recently, new methods such as linker labilization for the construction of HP‐MOFs have emerged. To further enrich the synthetic toolkit of MOFs, we report a controlled photolytic removal of linkers to create mesopores within microporous MOFs at tens of milliseconds. Ultraviolet (UV) laser has been applied to eliminate "photolabile" linkers without affecting the overall crystallinity and integrity of the original framework. Presumably, the creation of mesopores can be attributed to the missing‐cluster defects, which can be tuned through varying the time of laser exposure and ratio of photolabile/robust linkers. Upon laser exposure, MOF crystals shrank while metal oxide nanoparticles formed giving rise to the HP‐MOFs. In addition, photolysis can also be utilized for the fabrication of complicated patterns with high precision, paving the way towards MOF lithography, which has enormous potential in sensing and catalysis. Abstract : Mesopores within microporous MOFs were generated in milliseconds by controlled photolytic removal of linkers. The photolabile linkers are eliminated by irradiation with a UV laser without affecting the overall crystallinity and integrity of the original framework.