Metal-organic frameworks (MOFs) are typically highlighted for their potential application in gas storage, separations and catalysis. In contrast, the unique prospects these porous and crystalline materials offer for application in electronic devices, although actively developed, are often underexposed. This review highlights the research aimed at the implementation of MOFs as an integral part of solid-state microelectronics. Manufacturing these devices will critically depend on the compatibility of MOFs with existing fabrication protocols and predominant standards. Therefore, it is important to focus in parallel on a fundamental understanding of the distinguishing properties of MOFs and eliminating fabrication-related obstacles for integration. The latter implies a shift from the microcrystalline powder synthesis in chemistry labs, towards film deposition and processing in a cleanroom environment. Both the fundamental and applied aspects of this two-pronged approach are discussed. Critical directions for future research are proposed in an updated high-level roadmap to stimulate the next steps towards MOF-based microelectronics within the community.

Integrating metal-organic frameworks (MOFs) in microelectronics has disruptive potential because of the unique properties of these microporous crystalline materials. Suitable film deposition methods are crucial to leverage MOFs in this field. Conventional solvent-based procedures, typically adapted from powder preparation routes, are incompatible with nanofabrication because of corrosion and contamination risks. We demonstrate a chemical vapour deposition process (MOF-CVD) that enables high-quality films of ZIF-8, a prototypical MOF material, with a uniform and controlled thickness, even on high-aspect-ratio features. Furthermore, we demonstrate how MOF-CVD enables previously inaccessible routes such as lift-off patterning and depositing MOF films on fragile features. The compatibility of MOF-CVD with existing infrastructure, both in research and production facilities, will greatly facilitate MOF integration in microelectronics. MOF-CVD is the first vapour-phase deposition method for any type of microporous crystalline network solid and marks a milestone in processing such materials.

Metal-organic frameworks (MOFs) are a class of crystalline materials that consist of metal ions and organic ligands linked together by coordination bonds. Because of their porosity and the possibility of combining large surface areas with pore characteristics that can be tailored, these solids show great promise for a wide range of applications. Although most applications currently under investigation are based on powdered solids, developing synthetic methods to prepare defect-free MOF layers will also enable applications based on selective permeation. Here, we demonstrate how the intrinsically hybrid nature of MOFs enables the self-completing growth of thin MOF layers. Moreover, these layers can be shaped as hollow capsules that demonstrate selective permeability directly related to the micropore size of the MOF crystallites forming the capsule wall. Such capsules effectively entrap guest species, and, in the future, could be applied in the development of selective microreactors containing molecular catalysts.

Functionalized linkers can greatly increase the activity of metal-organic framework (MOF) catalysts with coordinatively unsaturated sites. A clear linear free-energy relationship (LFER) was found between Hammett σ(m) values of the linker substituents X and the rate k(X) of a carbonyl-ene reaction. This is the first LFER ever observed for MOF catalysts. A 56-fold increase in rate was found when the substituent is a nitro group.

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The amalgamation of different disciplines is at the heart of reticular chemistry and has broadened the boundaries of chemistry by opening up an infinite space of chemical composition, structure, and material properties. Reticular design has enabled the precise prediction of crystalline framework structures, tunability of chemical composition, incorporation of various functionalities onto the framework backbone, and as a consequence, fine‐tuning of metal–organic framework (MOF) and covalent organic framework (COF) properties beyond that of any other material class. Leveraging the unique properties of reticular materials has resulted in significant advances from both a fundamental and an applied perspective. Here, we wish to review the milestones in MOF and COF research and give a critical view on progress in their real‐world applications. Finally, we briefly discuss the major challenges in the field that need to be addressed to pave the way for industrial applications.

After controlled pretreatment, some Zr-terephthalate metal-organic frameworks are highly selective catalysts for the cross-aldol condensation between benzaldehyde and heptanal. The proximity of Lewis acid and base sites in the amino-functionalized UiO-66(NH(2)) material further raises the reaction yields.

Computer-aided fabrication technologies combined with simulation and data processing approaches are changing our way of manufacturing and designing functional objects. Also in the field of catalytic technology and chemical engineering the impact of additive manufacturing, also referred to as 3D printing, is steadily increasing thanks to a rapidly decreasing equipment threshold. Although still in an early stage, the rapid and seamless transition between digital data and physical objects enabled by these fabrication tools will benefit both research and manufacture of reactors and structured catalysts. Additive manufacturing closes the gap between theory and experiment, by enabling accurate fabrication of geometries optimized through computational fluid dynamics and the experimental evaluation of their properties. This review highlights the research using 3D printing and computational modeling as digital tools for the design and fabrication of reactors and structured catalysts. The goal of this contribution is to stimulate interactions at the crossroads of chemistry and materials science on the one hand and digital fabrication and computational modeling on the other.