Abstract
Metal‐organic frameworks (MOFs) have been in the spotlight for a number of years due to their chemical and topological versatility. As MOF research has progressed, highly functionalised materials have become desirable for specific applications, and in many cases the limitations of direct synthesis have been realised. This has resulted in the search for alternative synthetic routes, with postsynthetic modification (PSM), a term used to collectively describe the functionalisation of pre‐synthesised MOFs whilst maintaining their desired characteristics, becoming a topic of interest. Advances in the scope of reactions performed are reported regularly; however reactions requiring harsh conditions can result in degradation of the framework. Zirconium‐based MOFs present high chemical, thermal and mechanical stabilities, offering wider opportunities for the scope of reaction conditions that can be tolerated, which has seen a number of successful examples reported. This microreview discusses pertinent examples of PSM resulting in enhanced properties for specific applications, alongside fundamental transformations, which are categorised broadly into covalent modifications, surface transformations, metalations, linker and metal exchange, and cluster modifications.
Highlights
Metal-organic frameworks (MOFs)[1] are multidimensional materials containing metal ions or metal ion clusters that are connected by bridging multidentate organic ligands
The tolerance of MOFs linked by ZrIV-based clusters[8] towards harsh chemical[9] and mechanical[10] conditions makes them ideal platforms for introducing functionality by postsynthetic modification (PSM), and this microreview will focus on the diverse range of both chemical transformations and modification protocols used to prepare materials with applications in mind
The large number of articles discussed within, and the even greater number of articles on Zr MOFs that appear in the literature, highlight the extensive efforts that are currently being focused on Zr MOFs, which stems in part from their high chemical and mechanical stabilities and their ease of manipulation that renders them ideal platforms for functionalisation by postsynthetic modification to access materials not achievable by direct synthetic techniques
Summary
Typically imparts permanent porosity that is advantageous for various applications, including gas capture and storage,[2] catalysis[3] and drug delivery.[4]. Ross Marshall is from South West Scotland and graduated from the University of Glasgow in 2013 with a BSc (Hons) in Chemistry. Ross performed his final year research project under the supervision of Dr Ross Forgan, before joining The Forgan Group as a PhD student. He is currently in the third year of his PhD, where he carries out research into the synthesis, characterisation and postsynthetic modification of Zr and Hf MOFs. Dr Ross Forgan is a Royal Society University Research Fellow and Reader in the School of Chemistry at the University of Glasgow. We will examine fundamental and pertinent examples of application-driven PSM of Zr MOFs, organised broadly by the following modification protocols: covalent transformation of pendant and integral functional groups, surface modification, metalation, linker exchange, metal exchange and modification of the inorganic cluster
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