Toward the Nobel Prize: Dissecting Fundamental Principles and Applications of MOF and COF Materials

Abstract

Scientists have long dreamed of synthesizing materials with precise molecular-level control over their internal structures—of achieving what nature does so effortlessly. This vision began to materialize with the advent of reticular chemistry, pioneered by Susumu Kitagawa, Richard Robson, and Omar Yaghi, whose contributions have recently been recognized with the Nobel Prize in Chemistry.[1] With this breakthrough, it suddenly became possible to design and control the internal architecture of materials with atomic precision, enabling both tailored porosity and finely tuned interactions with guest molecules. The reticular chemistry of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) is now practiced with a degree of precision that rivals long-established methods in synthetic chemistry. The variation in composition and precise functionalization of these frameworks allows their properties to be controlled in all dimensions. In other words, the practical foundations of reticular chemistry now firmly support the exploitation of an almost limitless library of organic and inorganic building units that can be linked into frameworks, and the correspondingly broad landscape of properties and societal applications that can be pursued. Reticular chemistry thus operates in an effectively infinite design space of composition, structure, property, and application, providing unprecedented freedom to create an extraordinary diversity of new porous materials. MOFs currently represent one of the most intensively investigated and versatile classes of porous materials. To date, more than 100 000 distinct MOF structures with over 120 topologies have been reported,[2] and more than 500 000 additional structures have been predicted.[3] These remarkable numbers reflect the intensive research activity in the field: ≈96 000 MOF-related publications appeared between 2005 and 2025, including ≈14 000 papers published in 2025 alone (Figure 1).[4] Moreover, MOF-databases continue to expand at a rapid pace. Repositories now include the Cambridge Structural Database (CSD) MOF subset 2023 (≈120 000 structures), the Computation-Ready Experimental (CoRE) MOF 2019 database (≈14 000 structures), and the pyrene-based MOF dataset 2019 (62 structures).[2, 5] Databases of putative MOFs have also grown substantially, including the hypothetical MOF (hMOF) database 2011 (137 953 structures), the Topologically Based Crystal Constructor (ToBaCCo) MOF database 2017 (13 512 structures), the Quantum MOF (QMOF) database 2022 (20 375 structures), and the ab initio REPEAT-charge MOF (ARC-MOF) database 2023 (280 000 structures) (Figure 1).[2, 5] The chemical diversity of MOF structures is equally impressive; more than 65 metals have already been incorporated into MOF structures (Figure 1), and recent advances have enabled the synthesis of new actinide-[6] and tantalum-based MOFs.[7] Attempts to synthesize osmium-containing MOFs have also been reported,[8, 9] although the crystallinity of these materials remains to be improved. This extensive chemical space is further enriched by the use of more than 10 000 distinct organic linkers, as cataloged by the DigiMOF database,[10] with the ten most commonly used linkers shown in Figure 1. Over the past three decades, the field of MOFs has witnessed several remarkable milestones (Figure 1): in terms of porosity, a foundational MOF property, DUT-60 (Zr) currently holds the record Brunauer–Emmett–Teller (BET) surface area (7839 m2 g−1), as well as the largest pore volume (5.02 cm3 g−1).[11] IRMOF-XI (Zn) has the largest reported pore diameter to date, at 98 Å,[12] while NU-1301 (U) stands as the lowest-density MOF known, with a density of just 0.124 g cm−3.[13] Recent synthetic efforts to create multivariate (MTV) MOFs – materials incorporating multiple functionalities within a single scaffold – have pushed compositional complexity to new levels, resulting in the incorporation of 14 different metals within MTV-MIL-121[14]