Metal–organic frameworks (MOFs) are a class of coordination polymers consisting of metal clusters, also known as secondary building units (SBUs), coordinated to organic ligands to form one-, two-, or three-dimensional, typically porous structures. The ligands may be referred to as "struts" or "linkers", such as 1,4-benzenedicarboxylic acid (H2bdc). More formally, a metal–organic framework is a potentially porous extended structure made from metal ions and organic linkers. An extended structure is a structure whose sub-units occur in a constant ratio and are arranged in a repeating pattern. MOFs are a subclass of coordination networks, which is a coordination compound extending, through repeating entities, in one dimension, but with cross-links between two or more individual chains, loops, or spiro-links, or a coordination compound extending through repeating coordination entities in two or three dimensions. Coordination networks further belong to coordination polymers, which is a coordination compound with repeating coordination entities extending in one, two, or three dimensions. Most of the reported MOFs are crystalline compounds, but they can be amorphous, or reflect other disordered phases. In most cases for MOFs, the pores are stable during the elimination of the guest molecules (often solvents) and could be refilled with other compounds. Because of this property, MOFs are of interest for the storage of gases such as hydrogen and carbon dioxide. Other possible applications of MOFs are in gas purification, in gas separation, in water remediation, in catalysis, as conducting solids and as supercapacitors. The synthesis and properties of MOFs constitute the primary focus of reticular chemistry (from Latin reticulum, "small net"). In contrast to MOFs, covalent organic frameworks (COFs) are made entirely from light elements (H, B, C, N, and O) with extended structures. Susumu Kitagawa, Richard Robson and Omar Yaghi were awarded the Nobel Prize in Chemistry in 2025 for their work on MOFs.
History The discovery of coordination polymers, or as later termed metal-organic frameworks, was a logical continuation of research on post-zeolite materials. In 1989 Richard Robson reported the first organic copper-based coordination network by complexation of anions with tetrahedral bridging ligands. Similar copper(I) coordination polymers have been synthesized in 1992 by Susumu Kitagawa, which contained pores with loosely bound acetone molecules, but the structure would collapse upon their removal. Further efforts were devoted to develop extended 3D porous networks that would be stable upon removal of guest molecule and would exhibit permanent porosity. In 1995, Omar M. Yaghi demonstrated interpenetrated 2-D structure with carboxylate-based linkers that remained stable upon guest removal and could re-adsorb specific aromatic molecules. Permanent porosity in 3-D coordination polymer was first demonstrated in 1997 by Susumu Kitagawa. A year later, Yaghi proposed a new synthetical concept that employs secondary building units (SBUs) — metal-carboxylate clusters that serve as rigid building blocks for constructing frameworks with permanent porosity. In 1999, Yaghi and colleagues used SBU approach to synthesize MOF-5 that consists of zinc oxide clusters and terephthalate linkers. MOF-5 exhibits strong bonds between metal centers and coordinating organic molecules and hence exhibits high thermal stability while maintaining high porosity..
The field experienced a rapid development in the following years as shown by the inflection point at the year 2000 in the figure on the right.
Structure MOFs are composed of two main components: an inorganic metal cluster (often referred to as a secondary-building unit or SBU) and an organic molecule called a linker. For this reason, the materials are often referred to as hybrid organic-inorganic materials. The organic units are typically mono-, di-, tri-, or tetravalent ligands. The choice of metal and linker dictates the structure and hence properties of the MOF. For example, the metal's coordination preference influences the size and shape of pores by dictating how many ligands can bind to the metal, and in which orientation.
To describe and organize the structures of MOFs, a system of nomenclature has been developed. Subunits of a MOF, called secondary building units (SBUs), can be described by topologies common to several structures. Each topology, also called a net, is assigned a symbol, consisting of three lower-case letters in bold. MOF-5, for example, has a pcu net. Attached to the SBUs are bridging ligands. For MOFs, typical bridging ligands are di- and tricarboxylic acids. These ligands typically have rigid backbones. Examples are benzene-1,4-dicarboxylic acid (H2bdc or terephthalic acid), biphenyl-4,4′-dicarboxylic acid (H2bpdc), and the tricarboxylic acid trimesic acid. A fundamental aspect in the development of MOFs is that their crystal structures can be determined by X-ray crystallographic techniques as often, many MOFs have good crystallinity allowing their 3D structures to be determined precisely. This has allowed to study reactions taking place within the MOF's channels, revealing the structures of reaction intermediates.
Synthesis
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