Nitric oxide (NO) is an important signaling molecule in biological systems, and as such, the ability of porous materials to reversibly adsorb NO is of interest for potential medical applications. Although certain metal-organic frameworks are known to bind NO reversibly at coordinatively unsaturated metal sites, the influence of the metal coordination environment on NO adsorption has not been studied in detail. Here, we examine NO adsorption in the frameworks Co₂Cl₂(bbta) (H₂bbta = 1H,5H-benzo(1,2-d:4,5-d')bistriazole) and Co₂(OH)₂(bbta) using gas adsorption, infrared spectroscopy, powder X-ray diffraction, and magnetometry. At room temperature, NO adsorbs reversibly in Co₂Cl₂(bbta) without electron transfer, with low temperature data supporting spin-crossover of the NO-bound cobalt(ii) centers of the material. In contrast, adsorption of low pressures of NO in Co₂(OH)₂(bbta) is accompanied by charge transfer from the cobalt(ii) centers to form a cobalt(iii)-NO^- adduct, as supported by diffraction and infrared spectroscopy data. At higher pressures of NO, characterization data indicate additional uptake of the gas and disproportionation of the bound NO to form a cobalt(iii)-nitro (NO₂ ^-) species and N₂O gas, a transformation that appears to be facilitated by secondary sphere hydrogen bonding interactions between the bound NO₂ ^- and framework hydroxo groups. These results provide a rare example of reductive NO binding in a cobalt-based metal-organic framework, and they demonstrate that NO uptake can be tuned by changing the primary and secondary coordination environment of the framework metal centers.

[This corrects the article DOI: 10.1039/D1SC03994F.].

Bio-inspired motifs for gas binding and small molecule activation can be used to design more selective adsorbents for gas separation applications. Here, we report an iron metal-organic framework, Fe-BTTri (Fe₃[(Fe₄Cl)₃(BTTri)₈]₂·18CH₃OH, H₃BTTri = 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene), that binds O₂ in a manner similar to hemoglobin and therefore results in highly selective O₂ binding. As confirmed by gas adsorption studies and Mössbauer and infrared spectroscopy data, the exposed iron sites in the framework reversibly adsorb substantial amounts of O₂ at low temperatures by converting between high-spin, square-pyramidal Fe(ii) centers in the activated material to low-spin, octahedral Fe(iii)-superoxide sites upon gas binding. This change in both oxidation state and spin state observed in Fe-BTTri leads to selective and readily reversible O₂ binding, with the highest reported O₂/N₂ selectivity for any iron-based framework.

Calcium coordination solids were synthesized and evaluated for delivery of olsalazine (H₄ olz), an anti-inflammatory compound used for treatment of ulcerative colitis. The materials include one-dimensional Ca(H₂ olz)⋅4 H₂ O chains, two-dimensional Ca(H₂ olz)⋅2 H₂ O sheets, and a three-dimensional metal-organic framework Ca(H₂ olz)⋅2DMF (DMF=N,N-dimethylformamide). The framework undergoes structural changes in response to solvent, forming a dense Ca(H₂ olz) phase when exposed to aqueous HCl. The compounds Ca(H₂ olz)⋅x H₂ O (x=0, 2, 4) were each pressed into pellets and exposed to simulated gastrointestinal fluids to mimic the passage of a pill from the acidic stomach to the pH-neutral intestines. All three calcium materials exhibited a delayed release of olsalazine relative to Na₂ (H₂ olz), the commercial formulation, illustrating how formulation of a drug within an extended coordination solid can serve to tune its solubility and performance.

Industrial processes prominently feature π-acidic gases, and an adsorbent capable of selectively interacting with these molecules could enable important chemical separations^1-4. Biological systems use accessible, reducing metal centres to bind and activate weakly π-acidic species, such as N₂, through backbonding interactions^5-7, and incorporating analogous moieties into a porous material should give rise to a similar adsorption mechanism for these gaseous substrates⁸. Here, we report a metal-organic framework featuring exposed vanadium(II) centres capable of back-donating electron density to weak π acids to successfully target π acidity for separation applications. This adsorption mechanism, together with a high concentration of available adsorption sites, results in record N₂ capacities and selectivities for the removal of N₂ from mixtures with CH₄, while further enabling olefin/paraffin separations at elevated temperatures. Ultimately, incorporating such π-basic metal centres into porous materials offers a handle for capturing and activating key molecular species within next-generation adsorbents.

A major challenge to the implementation of artificial photosynthesis (AP), in which fuels are produced from abundant materials (water and carbon dioxide) in an electrochemical cell through the action of sunlight, is the discovery of active, inexpensive, safe, and stable catalysts for the oxygen evolution reaction (OER). Multimetallic molecular catalysts, inspired by the natural photosynthetic enzyme, can provide important guidance for catalyst design, but the necessary mechanistic understanding has been elusive. In particular, fundamental transformations for reactive intermediates are difficult to observe, and well-defined molecular models of such species are highly prone to decomposition by intermolecular aggregation. Here, we present a general strategy for stabilization of the molecular cobalt-oxo cubane core (Co₄O₄) by immobilizing it as part of metal-organic frameworks, thus preventing intermolecular pathways of catalyst decomposition. These materials retain the OER activity and mechanism of the molecular Co₄O₄ analog yet demonstrate unprecedented long-term stability at pH 14. The organic linkers of the framework allow for chemical fine-tuning of activity and stability and, perhaps most importantly, provide "matrix isolation" that allows for observation and stabilization of intermediates in the water-splitting pathway.

The design of stable adsorbents capable of selectively capturing dioxygen with a high reversible capacity is a crucial goal in functional materials development. Drawing inspiration from biological O₂ carriers, we demonstrate that coupling metal-based electron transfer with secondary coordination sphere effects in the metal-organic framework Co₂(OH)₂(bbta) (H₂bbta = 1H,5H-benzo(1,2-d:4,5-d')bistriazole) leads to strong and reversible adsorption of O₂. In particular, moderate-strength hydrogen bonding stabilizes a cobalt(III)-superoxo species formed upon O₂ adsorption. Notably, O₂-binding in this material weakens as a function of loading, as a result of negative cooperativity arising from electronic effects within the extended framework lattice. This unprecedented behavior extends the tunable properties that can be used to design metal-organic frameworks for adsorption-based applications.

Leveraging molecular-level controls to enhance CO₂ capture in solid-state materials has received tremendous attention in recent years. Here, a new class of hybrid nanomaterials constructed from intrinsically porous γ-Mg(BH₄ )₂ nanocrystals and reduced graphene oxide (MBHg) is described. These nanomaterials exhibit kinetically controlled, irreversible CO₂ uptake profiles with high uptake capacities (>19.9 mmol g^-1 ) at low partial pressures and temperatures between 40 and 100 °C. Systematic experiments and first-principles calculations reveal the mechanism of reaction between CO₂ and MBHg and unveil the role of chemically activated, metastable (BH₃ -HCOO)^- centers that display more thermodynamically favorable reaction and potentially faster reaction kinetics than the parent BH₄ ^- centers. Overall, it is demonstrated that size reduction to the nanoscale regime and the generation of reactive, metastable intermediates improve the CO₂ uptake properties in metal borohydride nanomaterials.

The widespread deployment of carbon capture and sequestration as a climate change mitigation strategy could be facilitated by the development of more energy-efficient adsorbents. Diamine-appended metal-organic frameworks of the type diamine-M₂(dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobpdc^4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) have shown promise for carbon-capture applications, although questions remain regarding the molecular mechanisms of CO₂ uptake in these materials. Here we leverage the crystallinity and tunability of this class of frameworks to perform a comprehensive study of CO₂ chemisorption. Using multinuclear nuclear magnetic resonance (NMR) spectroscopy experiments and van-der-Waals-corrected density functional theory (DFT) calculations for 13 diamine-M₂(dobpdc) variants, we demonstrate that the canonical CO₂ chemisorption products, ammonium carbamate chains and carbamic acid pairs, can be readily distinguished and that ammonium carbamate chain formation dominates for diamine-Mg₂(dobpdc) materials. In addition, we elucidate a new chemisorption mechanism in the material dmpn-Mg₂(dobpdc) (dmpn = 2,2-dimethyl-1,3-diaminopropane), which involves the formation of a 1:1 mixture of ammonium carbamate and carbamic acid and accounts for the unusual adsorption properties of this material. Finally, we show that the presence of water plays an important role in directing the mechanisms for CO₂ uptake in diamine-M₂(dobpdc) materials. Overall, our combined NMR and DFT approach enables a thorough depiction and understanding of CO₂ adsorption within diamine-M₂(dobpdc) compounds, which may aid similar studies in other amine-functionalized adsorbents in the future.