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Rare metal-organic framework (MOF) minerals stepanovite and zhemchuzhnikovite can exhibit properties comparable to known oxalate MOF proton conductors, including high proton conductivity over a range of relative humidities at 25 °C, and retention of the framework structure upon thermal dehydration. They also have high thermodynamic stability, with a pronounced stabilizing effect of substituting aluminium for iron, illustrating a simple design to access stable, highly proton-conductive MOFs without using complex organic ligands.

We demonstrate the use of ball milling mechanochemistry for rapid, simple, and materials-efficient synthesis of the organic mineral paceite CaCu(OAc)4·6H2O (where OAc- is the acetate ion), composed of coordination polymer chains containing alternating Ca2+ and Cu2+ ions, as well as its cadmium-based analogue CaCd(OAc)4·6H2O. While the synthesis of paceite in aqueous solutions requires a high excess of the copper precursor, mechanochemistry permits the use of stoichiometric amounts of reagents, as well as the use of poorly soluble and readily accessible calcium carbonate or hydroxide reactants. As established by thermochemical measurements, enthalpies of formation of both synthetic paceite and its cadmium analogue relevant to the mechanochemical reactions are highly exothermic. Reactions can also be conducted using accelerated aging, a synthetic technique that mimics geological processes of mineral weathering. Accelerated aging reactivity involving copper(II) acetate monohydrate (hoganite) and calcium carbonate (calcite) provides a potential explanation of how complex organic minerals like paceite could form in a geological environment.

The "disappearing polymorph" phenomenon is well established in organic solids, and has had a profound effect in pharmaceutical materials science. The first example of this effect in metal-containing systems in general, and in coordination-network solids in particular, is here reported. Specifically, attempts to mechanochemically synthesize a known interpenetrated diamondoid (dia) mercury(II) imidazolate metal-organic framework (MOF) yielded a novel, more stable polymorph based on square-grid (sql) layers. Simultaneously, the dia-form was found to be highly elusive, observed only as a short-lived intermediate in monitoring solvent-free synthesis and not at all from solution. The destabilization of a dense dia-framework relative to a lower dimensionality one is in contrast to the behavior of other imidazolate MOFs, with periodic density functional theory (DFT) calculations showing that it arises from weak interactions, including structure-stabilizing agostic C-H⋅⋅⋅Hg contacts. While providing a new link between MOFs and crystal engineering of organic solids, these findings highlight a possible role for agostic interactions in directing topology and stability of MOF polymorphs., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The recent discovery of minerals with metal-organic framework (MOF) structures has challenged the view of MOFs as purely synthetic materials. At the same time, the application of geo-inspired synthetic methodologies, such as accelerated ageing and pseudomorphic replication, has enabled a cleaner, more environmentally friendly synthesis of MOFs from mineral-like feedstocks, as well as the assembly of materials with structure controlled at both micro- and meso-scales. These almost concomitant developments have highlighted the previously unknown relationships between geology and MOF chemistry. Here, we outline examples of MOF structures found in minerals, and note geologically inspired approaches to MOF synthesis, as a means to highlight how the emergent geomimetic concepts in MOF chemistry can lead to advances in the design and synthesis of MOFs. This article is part of the theme issue 'Mineralomimesis: natural and synthetic frameworks in science and technology'.