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Porous isoreticular non-metal organic frameworks. | LitMetric

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Article Abstract

Metal-organic frameworks (MOFs) are useful synthetic materials that are built by the programmed assembly of metal nodes and organic linkers. The success of MOFs results from the isoreticular principle, which allows families of structurally analogous frameworks to be built in a predictable way. This relies on directional coordinate covalent bonding to define the framework geometry. However, isoreticular strategies do not translate to other common crystalline solids, such as organic salts, in which the intermolecular ionic bonding is less directional. Here we show that chemical knowledge can be combined with computational crystal-structure prediction (CSP) to design porous organic ammonium halide salts that contain no metals. The nodes in these salt frameworks are tightly packed ionic clusters that direct the materials to crystallize in specific ways, as demonstrated by the presence of well-defined spikes of low-energy, low-density isoreticular structures on the predicted lattice energy landscapes. These energy landscapes allow us to select combinations of cations and anions that will form thermodynamically stable, porous salt frameworks with channel sizes, functionalities and geometries that can be predicted a priori. Some of these porous salts adsorb molecular guests such as iodine in quantities that exceed those of most MOFs, and this could be useful for applications such as radio-iodine capture. More generally, the synthesis of these salts is scalable, involving simple acid-base neutralization, and the strategy makes it possible to create a family of non-metal organic frameworks that combine high ionic charge density with permanent porosity.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11153147PMC
http://dx.doi.org/10.1038/s41586-024-07353-9DOI Listing

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