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.

The current interest in porous crystalline metal-organic frameworks (MOFs) [1] is largely due to their wide range of compositions and structure types with low framework densities, their tunability, and the possibility of accessible, coordinatively unsaturated metal sites (CUS). The existence of CUS can strongly modify interactions with gases [2] or liquid adsorbates, [3] and is thus of particular importance gas storage and separations.The redox properties of transition-metal-substituted zeolites and mesoporous materials have been extensively studied and used for selective catalysis in liquid-phase oxidation, [4] removal of nitrogen oxides, [5] and photocatalytic reactions.[6]These features are very rare for MOFs containing 3d metals, in particular with respect to the reducibility of the framework metal ions. [7] For this reason, we examine herein both the conditions of generation of iron CUS with mixed valence Fe II

Christian Diercks studied chemistry at the University of Heidelberg and carried out undergraduate research in the group of Prof. Jean-Pierre Sauvage at the University of Strasbourg (France), as well as at Northwestern University (USA) under the guidance of Sir James Fraser Stoddart. He obtained his Ph.D. from UC Berkeley under the mentorship of Prof. Omar M. Yaghi in 2018 for his work on covalent organic frameworks. Currently,hei sapostdoctoral researcher in the group of Prof. Peter G. Schultz at the Scripps Research Institute, working on adding new chemistries to the processes of the central dogma of molecular biology.

Reticular chemistry is a growing field of science with a multitude of practitioners with diverse frames of thinking, making the need for standard practices and quality indicators ever more compelling.

We give a comprehensive overview of how the morphology control is an effective and versatile way to control the physicochemical properties of metal oxides that can be transferred to metal–organic frameworks and porous carbon materials.

The development of hybrid nanomaterials mimicking antifreeze proteins that can modulate/inhibit the growth of ice crystals for cell/tissue cryopreservation has attracted increasing interests. Herein, we describe the first utilization of zirconium (Zr)-based metal−organic framework (MOF) nanoparticles (NPs) with well-defined surface chemistries for the cryopreservation of red blood cells (RBCs) without the need of any (toxic) organic solvents. Distinguishing features of this cryoprotective approach include the exceptional water stability, low hemolytic activity, and the long periodic arrangement of organic linkers on the surface of MOF NPs, which provide a precise spacing of hydrogen donors to recognize and match the ice crystal planes. Five kinds of Zr-based MOF NPs, with different pore size, surface chemistry, and framework topologies, were used for the cryoprotection of RBCs. A "splat" assay confirmed that MOF NPs not only exhibited ice recrystallization inhibition activities but also acted as a "catalyst" to accelerate the melting of ice crystals. The human RBC cryopreservation tests displayed RBC recoveries of up to ∼40%, which is higher than that obtained via commonly used hydroxyethyl starch polymers. This cryopreservation approach will inspire the design and utilization of MOF-derived nanoarchitectures for the effective cryopreservation of various cell types as well as tissue samples.

Porous silica-based materials have burgeoning applications ranging from fillers and additives, to adsorbents, catalysts, and recently therapeutic agents and vaccines in nanomedicine. The preponderance of these materials is made by sol-gel processing wherein soluble silica precursors are reacted to form amorphous networks composed of siloxane bonds. The facile sol-gel approach allows for an unlimited variety of binary tertiary and more complex chemical compositions including organic ligands and networks resulting in so-called organic-inorganic hybrid materials. Here, a brief review of the recent progress in sol-gel-derived silica materials prepared as particles, thin films, biosilica/silica bioreplicas (of molecules, cells and organisms), and their related preparation, properties, and bioapplications is provided. First, it highlights the recent achievements of mesoporous silica nanoparticles in biomedical applications, including therapeutic agent delivery, multimodal imaging and theranostics, and bone tissue engineering and repair. Second, the research in evaporation-induced self-assembly (EISA)-based mesostructured silica thin films and cell-directed EISA in bio/nano interfaces for various bioapplications, such as bioactive coatings, biosensing, and living cell immobilization, has been reviewed. Third, the pioneering work in biomimetic silicification/ immobilization of biomolecules and bio-organisms and silica bioreplication of complex bio-organisms is summarized. Finally, it is concluded with personal perspectives on the directions of future work on this field. In 1846, Ebelmen synthesized tetraethylorthosilicate (TEOS) from SiCl 4 and ethanol and exposed it to water forming a transparent glassy material upon gelation and drying (now recognized to be a microporous xerogel). In 1864, the term "sol-gel" was first proposed by Graham during his work on silica sols. [2] In 1912-1915, Patrick developed an economically viable and rapid sol-gel process to mass-produce silica gel from sodium silicate (Na 2 SiO 3). And in 1931, Kistler reported the first synthesis of a highly porous silica (SiO 2) form, termed as "aerogel," which was a porous ultralight material derived from hydrolytic polycondensation of silicic acid (Si(OH) 4) to form a gel followed by supercritical drying to avoid drying shrinkage. [3] All of these efforts can be regarded as the beginning of modern sol-gel based silica materials, which are now ripening for wide range of applications, including the two pillars of the chemistry practice (synthesis and analysis), protective coatings, adsorption, chromatography, separation, biotechnology, energy conservation, cultural heritage restoration, and environmental remediation as well as many other fields of contemporary technology. [4] Based on the breakthroughs in synthesis, the recent two decades have witnessed an exponential increase in research of sol-gel-based silica materials for biomedical applications. Silica is inherently compatible with biological systems and was accepted as "Generally Recognized As Saf...

Reticular chemistry operates in an infinite space of compositions, structures, properties, and applications. Although great progress has been made in exploring this space through the development of metal-organic frameworks and covalent organic frameworks, there remains a gap between what we foresee as being possible and what can actually be accomplished with the current tools and methods. The establishment of digital reticular chemistry, where digital tools are deployed, in particular laboratory robotics and artificial intelligence, will fundamentally change the current workflow to enable discovery of this untapped chemical space and to go beyond the limits of human capacity. In so doing, long-standing challenges in reticular chemistry can finally be addressed faster and better, and more significantly, new questions, unimagined before digitization, can be articulated. The interface between human and ''machine'' is an integral part of this endeavor and one whose quality is critical to uncovering science transcending intellectual and physical borders.Scheme 1. Tools for Developing Digital Reticular Chemistry