Amorphous Metal–Organic Frameworks

Crystalline metal-organic frameworks (MOFs) are porous frameworks comprising an infinite array of metal nodes connected by organic linkers. The number of novel MOF structures reported per year is now in excess of 6000, despite significant increases in the complexity of both component units and molecular networks. Their regularly repeating structures give rise to chemically variable porous architectures, which have been studied extensively due to their sorption and separation potential. More recently, catalytic applications have been proposed that make use of their chemical tunability, while reports of negative linear compressibility and negative thermal expansion have further expanded interest in the field. Amorphous metal-organic frameworks (aMOFs) retain the basic building blocks and connectivity of their crystalline counterparts, though they lack any long-range periodic order. Aperiodic arrangements of atoms result in their X-ray diffraction patterns being dominated by broad "humps" caused by diffuse scattering and thus they are largely indistinguishable from one another. Amorphous MOFs offer many exciting opportunities for practical application, either as novel functional materials themselves or facilitating other processes, though the domain is largely unexplored (total aMOF reported structures amounting to under 30). Specifically, the use of crystalline MOFs to detect harmful guest species before subsequent stress-induced collapse and guest immobilization is of considerable interest, while functional luminescent and optically active glass-like materials may also be prepared in this manner. The ion transporting capacity of crystalline MOFs might be improved during partial structural collapse, while there are possibilities of preparing superstrong glasses and hybrid liquids during thermal amorphization. The tuning of release times of MOF drug delivery vehicles by partial structural collapse may be possible, and aMOFs are often more mechanically robust than crystalline materials, which is of importance for industrial applications. In this Account, we describe the preparation of aMOFs by introduction of disorder into their parent crystalline frameworks through heating, pressure (both hydrostatic and nonhydrostatic), and ball-milling. The main method of characterizing these amorphous materials (analysis of the pair distribution function) is summarized, alongside complementary techniques such as Raman spectroscopy. Detailed investigations into their properties (both chemical and mechanical) are compiled and compared with those of crystalline MOFs, while the impact of the field on the processing techniques used for crystalline MOF powders is also assessed. Crucially, the benefits amorphization may bring to existing proposed MOF applications are detailed, alongside the possibilities and research directions afforded by the combination of the unique properties of the amorphous domain with the versatility of MOF chemistry.