Metal-organic frameworks (MOFs) are a class of highly regular, crystalline, porous material which are formed by the linking of metal centers with multitopic organic linkers. Thermal processability is crucial for the commercialization and large-scale fabrication of MOFs into usable forms factors, but due to their highly crystalline nature melt processing techniques of MOFs are virtually non-existent. Indeed, such is the reason for the ubiquity of synthetic polymers; thermal processing is facile and bulk structures of nearly infinite complex shapes, sizes, and thicknesses can be achieved. However, commercially available polymers have no inherent chemical function, unlike MOFs which are capable of catalyzing an enormous variety of reactions, have tremendous storage capacity due to their massive surface areas, and are highly efficient separation membranes at the molecular level. Combining the exciting potential of MOFs as high-performance materials with the facile processability of conventional polymers into a single hybrid material would draw MOFs significantly closer to real-world implementation than their current place as largely an academic curiosity. Herein, we discuss the formation of MOFs directly from polymer-based ligands (polyMOFs) and show that block polymers containing both ligand- and morphology-directing blocks allow for exquisite control of the material morphology. Subsequently, we demonstrate the ability to convert polymers containing benzenedicarboxylate ligands into polyMOFs via a solvent-free synthetic procedure bringing these materials closer to real-world implementation.

PolyMOFs: Hybridization of polymers and metal–organic frameworks as a route towards thermally processable MOFs

2019 Fall National Meeting

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