Authors: Stefan Wuttke
Source: Advanced Materials (article, 2025-12-01)
Field: Chemistry — Inorganic Chemistry

Toward the Nobel Prize: Dissecting Fundamental Principles and Applications of MOF and COF Materials 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] and an impressive 36 distinct organic linkers within the MOF-5 framework.[15] These examples showcase the immense versatility and multifunctionality achievable through reticular chemistry. A particularly fascinating characteristic of many MOFs is their intrinsic flexibility, allowing their frameworks to contract/expand reversibly in response to external stimuli (e.g., guest molecules, temperature, or pressure). Currently, MIL-88C (Fe) exhibits the largest known unit-cell volume expansion, reaching up to 270%.[16] Structural complexity has also advanced significantly, with a remarkable degree of interpenetration of 32 achieved in the chiral MOF 32-Dia (Cu).[17] Progress in crystallization has likewise been substantial. MIRO-101 (Zn) represents the largest MOF single crystal grown to date, with an impressive size of ≈8 mm.[18] Beyond academic interest, MOFs are increasingly transitioning into commercially viable technologies.[19] There are now more than 45 start-up companies worldwide developing scalable MOF synthesis protocols (from kilogram- to ton-scale production) and translating the most promising MOF-based applications into industrial processes (Figure 1).[20] For industrial adoption, a MOF must demonstrate stability and high performance for a specific application, as well as the ability to be produced at a large scale and processed into practical forms such as pellets, thin films, or beads.[20-22] It must also be recyclable, with techno-economic analyses confirming favorable production costs and viable pathways to profitability.[20, 21] Equally important are performance–sustainability trade-off assessments, which ensure that exceptional material performance aligns with sustainable green practices.[23-25] Although a wide range of potential applications is currently being explored in academic research, only a few have achieved high technology readiness levels in industry. Among these, gas capture, separation, and storage, as well as atmospheric water harvesting, currently stand out as the most commercially mature areas.[20] In the critical area of gas capture and separation,[26-28] CALF-20 (Zn) has demonstrated exceptional performance in capturing CO2 from wet acid flue gas in real-world industrial conditions, successfully removing ≈1 tonne of CO2 per day from the flue gas of a Canadian cement plant.[29] This achievement is further amplified by BASF's initiative to upscale CALF-20 (Zn) production to 100 tonnes per year, representing one of the largest industrial manufacturing commitments to a MOF to date.[30] Beyond CO2 capture, MOFs are becoming strategically important for the removal, safe handling, and storage of hazardous gases. NuMat's ION-X technology enables the sub-atmospherically delivery and storage of hazardous dopant gases such as arsine, phosphine, and boron trifluoride, which are essential in the electronics industry.[31] A particularly prominent application of MOFs is atmospheric water harvesting, where they outperform commercial adsorbents such as silica gel and zeolites. Their ability to efficiently capture and release water using only solar energy has earned them a place among the world's top promising technologies for addressing water scarcity.[32, 33] MOF-303 (Al) is now being commercialized, owing to the abundance and low cost of aluminium as well as the material's excellent water harvesting performance: it can yield up to 0.7 L of water per kilogram of MOF per day under desert conditions.[34] Another compelling application is their integration into air conditioning systems for dehumidification, pioneered by Transaera.[35] In this approach, MOFs passively capture moisture from incoming air, after which waste heat is used to regenerate the material, enabling continuous and energy-efficient operation. In contrast to MOFs, COFs have been explored far less extensively, with fewer than 1000 structures reported to date; however, publications on COF discovery have grown exponentially in recent years (Figure 1). COFs are constructed entirely from light elements—typically hydrogen, carbon, nitrogen, oxygen, boron, sulfur, and silicon—using a variety of robust linkage chemistries, as illustrated in Figure 2. Key COF databases include the CoRE COF 2017 set (187 structures), the CURATED COFs 2019/2020 collection (648 structures), and the hypothetical COFs for Carbon Capture 2020 database (69 000 structures) (Figure 2).[5] Several notable milestones have been achieved within the COF field (Figure 2). The highest BET surface area so far is 5083 m2 g−1 for DBA-3D-COF-1,[36] while COF-108 holds the record for the largest pore volume at 5.4 cm3 g−1.[37] Further highlights include TUS-64, which exhibits the largest pore diameter among all 3D COFs at 47 Å and an exceptionally low density of 0.106 g cm−3.[38] A remarkable breakthrough occurred in 2016 with the synthesis of the first woven COF, COF-505, distinguished by its helical organic threads and woven topology.[39] Beyond these unique structural motifs, COFs have demonstrated intrinsic flexibility.[40] Notably, COF-303 exhibits the largest known expansion upon guest adsorption, with a 50% increase in unit-cell volume and a three-fold increase in channel size.[41] Advances in COF crystallization have also been significant: crystals of COFTP-Py up to 0.2 mm in size have been grown in supercritical CO2.[42] Despite these significant scientific achievements, industrial translation of COFs remains in its nascent stage. Only a small number of start-up companies are currently active, primarily targeting applications in gas storage and separation, highlighting both the challenges and the substantial future potential of this emerging class of materials.[19] This special issue is organized into two key chapters: the first highlights recent trends in the fundamental principles, scientific advancements, and commercialization of reticular materials, while the second provides a fresh perspective on emerging applications of MOFs and COFs. MOF research has advanced at a breathtaking pace over the past three decades, prompting a number of important questions of broad interest to the scientific community: How many MOF, COF, and HOF structures have been reported in this period? What databases now exist for reticular materials? How reproducible are published results? What challenges impede the translation of laboratory discoveries into industrial practice? What are the community's views on reporting guidelines? Which scientific and industrial milestones have shaped the field? What networking opportunities are available? What feedback has the community offered, and what are the future prospects? The perspective by Desai, Ettlinger et al., “Retrospective Review on Reticular Materials: Facts and Figures Over the Last 30 Years” (https://doi.org/10.1002/adma.202414736), provides an exceptionally valuable resource in addressing these questions. Drawing on detailed statistics gathered from 228 active researchers, the authors offer a comprehensive analysis that illuminates the community's research needs, potential challenges, and anticipated future directions. Understanding the fundamental principles that govern MOF construction is essential for the rational design of new frameworks with targeted structures and properties to meet specific needs. Reticular design provides a powerful conceptual foundation, offering guidance on how certain nodes, nets, building units, and coordination pathways can be combined to generate predictable and versatile MOF architectures—moving beyond conventional trial-and-error synthesis. The review by Guillerm, Eddaoudi et al., “From Elementary to Advanced Design of Functional Metal–Organic Frameworks: A User Guide to Deciphering the Reticular Chemistry Toolbox” (https://doi.org/10.1002/adma.202414153), provides comprehensive overview of the fundamental design principles that have been developed over the past 30 years, as along with innovative strategies that have emerged more recently. Topics include widely used approaches such as the molecular building block method and axial-to-axial pillaring, as well as more elaborate strategies involving supermolecular building blocks, building layers, and merged-net strategies for generating highly connected MOFs. The review also covers the geometry-mismatch strategy for constructing novel materials with unique zeolitic structures. To further empower MOF researchers with computational tools for the discovery of reticular materials, the article by Darù, Gagliardi et al., “Symmetry is the Key to the Design of Reticular Frameworks” (https://doi.org/10.1002/adma.202414617), introduces a computational workflow that predicts MOF and COF structures based solely on the connectivity and symmetry of node and linker building blocks. This platform is available online for use by the broader research community. Another essential dimension of MOF design lies in the realm of supramolecular interactions. The review by Casañ, Champness et al., “Supramolecular Chemistry in Metal–Organic Framework Materials” (https://doi.org/10.1002/adma.202414509), highlights the pivotal role of supramolecular chemistry in shaping MOF synthesis, structure, and function. By revealing how supramolecular principles govern reactivity, framework dynamics, and responsive behaviour, the authors position supramolecular chemistry as a unifying foundation for the rational design and functional diversification of reticular materials. The soft nature of MOFs formed by coordination bonds distinguishes them from other classes of porous materials, endowing certain frameworks with remarkable flexibility in response to external stimuli. This dynamic behavior enables responsive adsorption, selective guest inclusion, and adaptive structural transformations, opening unique opportunities for advanced functional materials. The review by Senkovska, Kaskel et al., “Adsorption and Separation by Flexible MOFs” (https://doi.org/10.1002/adma.202414724), presents a focused overview of how framework flexibility governs gas uptake, selectivity, and working capacity. It highlights the importance of single-gas isotherm analysis and appropriate adsorption conditions in designing effective separation experiments, while also identifying key challenges that currently hinder the practical deployment of flexible MOF adsorbents. The research article by Garzón, Gastaldo et al., “Structural Control of Photoconductivity in a Flexible Titanium-Organic Framework” (https://doi.org/10.1002/adma.202412045), expands the family of flexible MOFs by introducing a new flexible titanium-based framework, MUV-35, capable of undergoing ≈40% volume compression. 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