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A series of structurally diverse alcoholamine- and alkoxyalkylamine-functionalized variants of the metal-organic framework Mg2 (dobpdc) are shown to adsorb CO2 selectively via cooperative chain-forming mechanisms. Solid-state NMR spectra and optimized structures obtained from van der Waals-corrected density functional theory calculations indicate that the adsorption profiles can be attributed to the formation of carbamic acid or ammonium carbamate chains that are stabilized by hydrogen bonding interactions within the framework pores. These findings significantly expand the scope of chemical functionalities that can be utilized to design cooperative CO2 adsorbents, providing further means of optimizing these powerful materials for energy-efficient CO2 separations.

The synthesis of amides from amines and carboxylic acids is the most widely carried out reaction in medicinal chemistry. Yet, most amide couplings are still conducted using stoichiometric reagents, leading to significant waste; few synthetic catalysts for this transformation have been adopted industrially due to their limited scope and/or poor recyclability. The majority of catalytic approaches focus on a single activation mode, such as enhancing the electrophilicity of the carboxylic acid partner using a Lewis acid. In contrast, nature effortlessly forges and breaks amide bonds using precise arrays of Lewis/Brønsted acidic and basic functional groups. Drawing inspiration from these systems, herein we report a simple defect engineering strategy to colocalize Lewis acidic Zr sites with other catalytically active species within porous metal-organic frameworks (MOFs). Specifically, the combination of pyridine N -oxide and Zr open metal sites within the defective framework MOF-808-py-Nox produces a heterogeneous catalyst that facilitates amide bond formation with broad functional group compatibility from amines and carboxylic acids, esters, or primary amides. Extensive density functional theory (DFT) calculations using cluster models support that the formation of a hydrogen-bonding network at the defect sites facilitates amide bond formation in this material. MOF-808-py-Nox can be recycled at least five times without losing significant crystallinity, porosity, or catalytic activity and can be employed in continuous flow. This defect engineering strategy can be potentially generalized to produce libraries of catalytically active MOFs with different combinations of colocalized functional groups.

The design and synthesis of photoactive metal-free 2D materials for selective heterogeneous photoredox catalysis continue to be challenging due to issues related to nonrecyclability, and limited photo- and chemical stability. Herein, we report the photocatalytic properties of a triazine-based porous COF, TRIPTA , which is found to be capable of facilitating both SET (single electron transfer) for photocatalytic reductive debromination of phenacyl bromide in absence of oxygen and generation of reactive oxygen species (ROS) for benzylamine photo-oxidation in the presence of oxygen, respectively, under visible light irradiation. Inspired by the latter results, we further systematically investigated different-sized benzylamine substrates in this single-component reaction and compared the results with an analogous COF ( Micro-COF-2 ) exhibiting a larger pore size. We observed a marked improvement in the conversion of larger-sized substrates with the latter COF, thereby demonstrating angstrom-level pore size-selective photocatalytic activity of COFs., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The reductive functionalization of inert substrates like chloroarenes is a critical yet challenging transformation relevant to both environmental remediation and organic synthesis. Combining electricity and light is an emerging approach to access the deeply reducing potentials required for single electron transfer to chloroarenes, yet this approach is held back by the poor stability and mechanistic ambiguity of current homogeneous systems. Incorporating redox-active moieties into insoluble organic materials represents a promising strategy to unlock new heterogeneous catalytic activity while improving catalyst stability. Herein, we demonstrate the first example of heterogeneous electrophotocatalysis using redox-active rylene diimide polymers for the reduction of chloroarenes. In particular, we find that the electrophotocatalytic activity varies significantly not just as a function of the rylene diimide but also of the redox-inactive polymer backbone. In particular, PTCDA-en , a flexible, non-conjugated perylenediimide polymer, outperforms all other tested materials as an electrophotocatalyst. Using transient absorption spectroscopy, we reveal that precomplexation between the closed-shell PTCDA-en 2- and the haloarene substrate is key to productive catalysis. Overall, our work represents the first example of heterogeneous electrophotocatalysis using an insoluble redox-active organic material and provides critical insights into how polymer structure dictates electrophotocatalytic activity in the solid state, guiding the development of next-generation heterogeneous (electro)photocatalysts for sustainable synthesis., Competing Interests: Conflict of interests: The authors declare no conflict of interest.

Carbon dioxide capture technologies are set to play a vital role in mitigating the current climate crisis. Solid-state 17 O NMR spectroscopy can provide key mechanistic insights that are crucial to effective sorbent development. In this work, we present the fundamental aspects and complexities for the study of hydroxide-based CO 2 capture systems by 17 O NMR. We perform static density functional theory (DFT) NMR calculations to assign peaks for general hydroxide CO 2 capture products, finding that 17 O NMR can readily distinguish bicarbonate, carbonate and water species. However, in application to CO 2 binding in two test case hydroxide-functionalised metal-organic frameworks (MOFs) - MFU-4l and KHCO 3 -cyclodextrin-MOF, we find that a dynamic treatment is necessary to obtain agreement between computational and experimental spectra. We therefore introduce a workflow that leverages machine-learning force fields to capture dynamics across multiple chemical exchange regimes, providing a significant improvement on static DFT predictions. In MFU-4l, we parameterise a two-component dynamic motion of the bicarbonate motif involving a rapid carbonyl seesaw motion and intermediate hydroxyl proton hopping. For KHCO 3 -CD-MOF, we combined experimental and modelling approaches to propose a new mixed carbonate-bicarbonate binding mechanism and thus, we open new avenues for the study and modelling of hydroxide-based CO 2 capture materials by 17 O NMR., (© 2024 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

Organic electrode materials are appealing candidates for a wide range of applications, including heterogeneous electrocatalysis and electrochemical energy storage. However, a narrow understanding of the structure-property relationships in these materials hinders the full realization of their potential. Herein, we investigate a family of insoluble perylenediimide (PDI) polymers to interrogate how backbone flexibility affects their thermodynamic and kinetic redox properties. We verify that the polymers generally access the highest percentage of redox-active groups with K + ions (vs Na + and Li + ) due to its small solvation shell/energy and favorable soft-soft interactions with reduced PDI species. Through cyclic voltammetry, we show that increasing the polymer flexibility does not minimize barriers to ion-insertion processes but rather increases the level of diffusion-limited processes. Further, we propose that the condensation of imides to iminoimides can truncate the imide polymer chain growth for certain diamine monomers, leading to greater polymer solubilization and reduced cycling stability. Together, our results provide insight into how polymer flexibility, ion-electrode interactions, and polymerization side reactions dictate the redox properties of PDI polymers, paving the way for the development of next-generation organic electrode materials.

The formation of carbon-carbon (C-C) bonds is a cornerstone of organic synthesis. Among various methods to construct Csp 2 -Csp 3 bonds, the reductive Heck reaction between (hetero)aryl halides and alkenes stands out due to its potential efficiency and broad substrate availability. However, traditional reductive Heck reactions are limited by the use of precious metal catalysts and/or limited aryl halide and alkene compatibility. Here, we present an electrochemically mediated, metal- and catalyst-free reductive Heck reaction that tolerates both unactivated (hetero)aryl halides and diverse alkenes such as vinyl boronates and silanes. Detailed electrochemical and deuterium-labeling studies support that this transformation likely proceeds through a paired electrolysis pathway, in which acid generated by the oxidation of N,N-diisopropylethylamine (DIPEA) at the anode intercepts an alkyl carbanion formed after radical-polar crossover at the cathode. As such, this approach offers a sustainable method for the construction of Csp 2 -Csp 3 bonds from (hetero)aryl halides and alkenes, paving the way for the development of other electrochemically mediated olefin difunctionalization reactions., (© 2024 Wiley-VCH GmbH.)

Covalent organic frameworks linked by carbon-carbon double bonds (C=C COFs) are an emerging class of crystalline, porous, and conjugated polymeric materials with potential applications in organic electronics, photocatalysis, and energy storage. Despite the rapidly growing interest in sp 2 carbon-conjugated COFs, only a small number of closely related condensation reactions have been successfully employed for their synthesis to date. Herein, we report the first example of a C=C COF, CORN-COF-1 (CORN=Cornell University), prepared by N-heterocyclic carbene (NHC) dimerization. In-depth characterization reveals that CORN-COF-1 possesses a two-dimensional layered structure and hexagonal guest-accessible pores decorated with a high density of strongly reducing tetraazafulvalene linkages. Exposure of CORN-COF-1 to tetracyanoethylene (TCNE, E 1/2 =0.13 V and -0.87 V vs. SCE) oxidizes the COF and encapsulates the radical anion TCNE⋅ - and the dianion TCNE 2- as guest molecules, as confirmed by spectroscopic and magnetic analysis. Notably, the reactive TCNE⋅ - radical anion, which generally dimerizes in the solid state, is uniquely stabilized within the pores of CORN-COF-1. Overall, our findings broaden the toolbox of reactions available for the synthesis of redox-active C=C COFs, paving the way for the design of novel materials., (© 2024 Wiley-VCH GmbH.)

Gases are essential for various applications relevant to human health, including in medicine, biomedical imaging, and pharmaceutical synthesis. However, gases are significantly more challenging to safely handle than liquids and solids. Herein, we review the use of porous materials, such as metal-organic frameworks (MOFs), zeolites, and silicas, to adsorb medicinally relevant gases and facilitate their handling as solids. Specific topics include the use of MOFs and zeolites to deliver H 2 S for therapeutic applications, 129 Xe for magnetic resonance imaging, O 2 for the treatment of cancer and hypoxia, and various gases for use in organic synthesis. This Perspective aims to bring together the organic, inorganic, medicinal, and materials chemistry communities to inspire the design of next-generation porous materials for the storage and delivery of medicinally relevant gases., (© 2024 Wiley-VCH GmbH.)

Hydrogen sulfide (H 2 S) is an endogenously produced gasotransmitter involved in many physiological processes that are integral to proper cellular functioning. Due to its profound anti-inflammatory and antioxidant properties, H 2 S plays important roles in preventing inflammatory skin disorders and improving wound healing. Transdermal H 2 S delivery is a therapeutically viable option for the management of such disorders. However, current small-molecule H 2 S donors are not optimally suited for transdermal delivery and typically generate electrophilic byproducts that may lead to undesired toxicity. Here, we demonstrate that H 2 S release from metal-organic frameworks (MOFs) bearing coordinatively unsaturated metal centers is a promising alternative for controlled transdermal delivery of H 2 S. Gas sorption measurements and powder X-ray diffraction (PXRD) studies of 11 MOFs support that the Mg-based framework Mg 2 (dobdc) (dobdc 4- = 2,5-dioxidobenzene-1,4-dicarboxylate) is uniquely well-suited for transdermal H 2 S delivery due to its strong yet reversible binding of H 2 S, high capacity (14.7 mmol/g at 1 bar and 25 °C), and lack of toxicity. In addition, Rietveld refinement of synchrotron PXRD data from H 2 S-dosed Mg 2 (dobdc) supports that the high H 2 S capacity of this framework arises due to the presence of three distinct binding sites. Last, we demonstrate that transdermal delivery of H 2 S from Mg 2 (dobdc) is sustained over a 24 h period through porcine skin. Not only is this significantly longer than sodium sulfide but this represents the first example of controlled transdermal delivery of pure H 2 S gas. Overall, H 2 S-loaded Mg 2 (dobdc) is an easily accessible, solid-state source of H 2 S, enabling safe storage and transdermal delivery of this therapeutically relevant gas.

Emissions reduction and greenhouse gas removal from the atmosphere are both necessary to achieve net-zero emissions and limit climate change 1 . There is thus a need for improved sorbents for the capture of carbon dioxide from the atmosphere, a process known as direct air capture. In particular, low-cost materials that can be regenerated at low temperatures would overcome the limitations of current technologies. In this work, we introduce a new class of designer sorbent materials known as 'charged-sorbents'. These materials are prepared through a battery-like charging process that accumulates ions in the pores of low-cost activated carbons, with the inserted ions then serving as sites for carbon dioxide adsorption. We use our charging process to accumulate reactive hydroxide ions in the pores of a carbon electrode, and find that the resulting sorbent material can rapidly capture carbon dioxide from ambient air by means of (bi)carbonate formation. Unlike traditional bulk carbonates, charged-sorbent regeneration can be achieved at low temperatures (90-100 °C) and the sorbent's conductive nature permits direct Joule heating regeneration 2,3 using renewable electricity. Given their highly tailorable pore environments and low cost, we anticipate that charged-sorbents will find numerous potential applications in chemical separations, catalysis and beyond., (© 2024. The Author(s).)

The selective halogenation of complex (hetero)aromatic systems is a critical yet challenging transformation that is relevant to medicinal chemistry, agriculture, and biomedical imaging. However, current methods are limited by toxic reagents, expensive homogeneous second- and third-row transition metal catalysts, or poor substrate tolerance. Herein, we demonstrate that porous metal-organic frameworks (MOFs) containing terminal Co(III) halide sites represent a rare and general class of heterogeneous catalysts for the controlled installation of chlorine and fluorine centers into electron-deficient (hetero)aryl bromides using simple metal halide salts. Mechanistic studies support that these halogen exchange (halex) reactions proceed via redox-neutral nucleophilic aromatic substitution (S N Ar) at the Co(III) sites. The MOF-based halex catalysts are recyclable, enable green halogenation with minimal waste generation, and facilitate halex in a continuous flow. Our findings represent the first example of S N Ar catalysis using MOFs, expanding the lexicon of synthetic transformations enabled by these materials.

Perfluorocompound (PFC) gases play vital roles in microelectronics processing. Requirements for ultra-high purities traditionally necessitate use of virgin sources and thereby hinder the capture, purification, and reuse of these costly gases. Most importantly, gaseous PFCs are incredibly potent greenhouse gases with atmospheric lifetimes on the order of 10 3 -10 4 years, and thus any environmental emissions have an outsized and prolonged impact on our climate. The development of sorbents that can capture PFC gases from industrial waste streams has lagged substantially behind the progress made over the last decade in capturing CO 2 from both point emission sources and directly from air. Herein, we show that the metal-organic framework Zn(fba) (fba 2- = 4,4'-(hexafluoroisopropylidene)bis-benzoate) displays an equilibrium selectivity for CF 4 adsorption over N 2 that surpasses those of all water-stable sorbents that have been reported for this separation. Selective adsorption of both CHF 3 and CH 4 over N 2 is also evident, demonstrating a general preference for tetrahedral C 1 gases. This selectivity is enabled by adsorption within narrow corrugated channels lined with ligand-based aryl rings, a site within this material that has not previously been realized as being accessible to guests. Analyses of adsorption kinetics and X-ray diffraction data are used to characterize sorption and diffusion of small adsorbates within these channels and strongly implicate rotation of the linker aryl rings as a gate that modulates transport of the C 1 gases through a crystallite. Multi-component breakthrough measurements demonstrate that Zn(fba) is able to resolve mixtures of CF 4 and N 2 under flow-through conditions. Taken together, this work illuminates the dynamic structure of Zn(fba), and also points toward general design principles that can enable large CF 4 selectivities in sorbents with more favorable kinetic profiles., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Diamine-appended Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) metal-organic frameworks are promising candidates for carbon capture that exhibit exceptional selectivities and high capacities for CO 2 . To date, CO 2 uptake in these materials has been shown to occur predominantly via a chemisorption mechanism involving CO 2 insertion at the amine-appended metal sites, a mechanism that limits the capacity of the material to ∼1 equiv of CO 2 per diamine. Herein, we report a new framework, pip2-Mg 2 (dobpdc) (pip2 = 1-(2-aminoethyl)piperidine), that exhibits two-step CO 2 uptake and achieves an unusually high CO 2 capacity approaching 1.5 CO 2 per diamine at saturation. Analysis of variable-pressure CO 2 uptake in the material using solid-state nuclear magnetic resonance (NMR) spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) reveals that pip2-Mg 2 (dobpdc) captures CO 2 via an unprecedented mechanism involving the initial insertion of CO 2 to form ammonium carbamate chains at half of the sites in the material, followed by tandem cooperative chemisorption and physisorption. Powder X-ray diffraction analysis, supported by van der Waals-corrected density functional theory, reveals that physisorbed CO 2 occupies a pocket formed by adjacent ammonium carbamate chains and the linker. Based on breakthrough and extended cycling experiments, pip2-Mg 2 (dobpdc) exhibits exceptional performance for CO 2 capture under conditions relevant to the separation of CO 2 from landfill gas. More broadly, these results highlight new opportunities for the fundamental design of diamine-Mg 2 (dobpdc) materials with even higher capacities than those predicted based on CO 2 chemisorption alone.

Electroactive materials are central to myriad applications, including energy storage, sensing, and catalysis. Compared to traditional inorganic electrode materials, redox-active organic materials such as porous organic polymers (POPs) and covalent organic frameworks (COFs) are emerging as promising alternatives due to their structural tunability, flexibility, sustainability, and compatibility with a range of electrolytes. Herein, we discuss the challenges and opportunities available for the use of redox-active organic materials in organoelectrochemistry, an emerging area in fine chemical synthesis. In particular, we highlight the utility of organic electrode materials in photoredox catalysis, electrochemical energy storage, and electrocatalysis and point to new directions needed to unlock their potential utility for organic synthesis. This Perspective aims to bring together the organic, electrochemistry, and polymer communities to design new heterogeneous electrocatalysts for the sustainable synthesis of complex molecules., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Metal-organic frameworks (MOFs) are porous, crystalline materials constructed from organic linkers and inorganic nodes with potential utility in gas separations, drug delivery, sensing, and catalysis. Small variations in MOF synthesis conditions can lead to a range of accessible frameworks with divergent chemical or photophysical properties. New methods to controllably access phases with tailored properties would broaden the scope of MOFs that can be reliably prepared for specific applications. Herein, we demonstrate that simply increasing the reaction concentration during the solvothermal synthesis of M 2 (dobdc) (M = Mg, Mn, Ni; dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate) MOFs unexpectedly leads to trapping of a new framework termed CORN-MOF-1 (CORN = Cornell University) instead. In-depth spectroscopic, crystallographic, and computational studies support that CORN-MOF-1 has a similar structure to M 2 (dobdc) but with partially protonated linkers and charge-balancing or coordinated formate groups in the pores. The resultant variation in linker spacings causes CORN-MOF-1 (Mg) to be strongly photoluminescent in the solid state, whereas H 4 dobdc and Mg 2 (dobdc) are weakly emissive due to excimer formation. In-depth photophysical studies suggest that CORN-MOF-1 (Mg) is the first MOF based on the H 2 dobdc 2- linker that likely does not emit via an excited state intramolecular proton transfer (ESIPT) pathway. In addition, CORN-MOF-1 variants can be converted into high-quality samples of the thermodynamic M 2 (dobdc) phases by heating in N,N -dimethylformamide (DMF). Overall, our findings support that high-concentration synthesis provides a straightforward method to identify new MOFs with properties distinct from known materials and to produce highly porous samples of MOFs, paving the way for the discovery and gram-scale synthesis of framework materials.

Metal-organic frameworks (MOFs) are porous, crystalline materials constructed from organic linkers and inorganic nodes that have attracted widespread interest due to their permanent porosity and highly modular structures. However, the large volumes of organic solvents and additives, long reaction times, and specialized equipment typically required to synthesize MOFs hinder their widespread adoption in both academia and industry. Recently, our lab has developed several user-friendly methods for the gram-scale (1-100 g) preparation of MOFs. Herein, we summarize our progress in the development of high-concentration solvothermal, mechanochemical, and ionothermal syntheses of MOFs, as well as in minimizing the amount of modulators required to prepare highly crystalline Zr-MOFs. To begin, we detail our work elucidating key features of acid modulation in Zr-MOFs to improve upon current dilute solvothermal syntheses. Choosing an optimal modulator maximizes the crystallinity and porosity of Zr-MOFs while minimizing the quantity of modulator needed, reducing the waste associated with MOF synthesis. By evaluating a range of modulators, we identify the p K a , size, and structural similarity of the modulator to the linker as controlling factors in modulating ability. In the following section, we describe two high-concentration solvothermal methods for the synthesis of Zr-MOFs and demonstrate their generality among a range of frameworks. We also target the M 2 (dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn, Cd; dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate) family of MOFs for high-concentration synthesis and introduce a two-step preparation of several variants that proceeds through a novel kinetic phase. The high-concentration methods we discuss produce MOFs on multi-gram scale with comparable properties to those prepared under traditional dilute solvothermal conditions. Next, to further curtail solvent waste and accelerate reaction times, we discuss the mechanochemical preparation of M 2 (dobdc) MOFs utilizing liquid amine additives in a planetary ball mill, which we also apply to the synthesis of two related salicylate frameworks. These samples exhibit comparable porosities to traditional dilute solvothermal samples but can be synthesized in just minutes, as opposed to days, and require under 1 mL of liquid additive to prepare ~0.5 g of material. In the following section, we discuss our efforts to avoid specialized equipment and eliminate solvent use entirely by employing ionothermal conditions to prepare a variety of azolate- and salicylate-based MOFs. Simply combining metal chloride (hydrate) salts with organic linkers at temperatures above the melting points of the salts affords high-quality framework materials. Further, ionothermal conditions enable the syntheses of two new Fe(III) M 2 (dobdc) derivatives that cannot be synthesized under normal solvothermal conditions. Last, as a demonstrative example, we discuss our efforts to synthesize 100 g of high-quality Mg 2 (dobdc) in a single batch using a high-concentration (1.0 M) hydrothermal synthesis. Our Account will be of significant interest to researchers aiming to prepare gram-scale quantities of MOFs for further study.

Single-electron transfer (SET) plays a critical role in many chemical processes, from organic synthesis to environmental remediation. However, the selective reduction of inert substrates (E p/2 <-2 V vs Fc/Fc + ), such as ubiquitous electron-neutral and electron-rich (hetero)aryl chlorides, remains a major challenge. Current approaches largely rely on catalyst photoexcitation to reach the necessary deeply reducing potentials or suffer from limited substrate scopes. Herein, we demonstrate that cumulenes-organic molecules with multiple consecutive double bonds-can function as catalytic redox mediators for the electroreductive radical borylation of (hetero)aryl chlorides at relatively mild cathodic potentials (approximately -1.9 V vs. Ag/AgCl) without the need for photoirradiation. Electrochemical, spectroscopic, and computational studies support that step-wise electron transfer from reduced cumulenes to electron-neutral chloroarenes is followed by thermodynamically favorable mesolytic cleavage of the aryl radical anion to generate the desired aryl radical intermediate. Our findings will guide the development of other sustainable, purely electroreductive radical transformations of inert molecules using organic redox mediators., (© 2023 Wiley-VCH GmbH.)

Fluorine is an increasingly common substituent in pharmaceuticals and agrochemicals because it improves the bioavailability and metabolic stability of organic molecules. Fluorinated gases represent intuitive building blocks for the late-stage installation of fluorinated groups, but they are generally overlooked because they require the use of specialized equipment. We report a general strategy for handling fluorinated gases as benchtop-stable solid reagents using metal-organic frameworks (MOFs). Gas-MOF reagents are prepared on gram-scale and used to facilitate fluorovinylation and fluoroalkylation reactions. Encapsulation of gas-MOF reagents within wax enables stable storage on the benchtop and controlled release into solution upon sonication, which represents a safer alternative to handling the gas directly. Furthermore, our approach enables high-throughput reaction development with these gases.

Diamine-appended Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) metal-organic frameworks have emerged as promising candidates for carbon capture owing to their exceptional CO 2 selectivities, high separation capacities, and step-shaped adsorption profiles, which arise from a unique cooperative adsorption mechanism resulting in the formation of ammonium carbamate chains. Materials appended with primary , secondary -diamines featuring bulky substituents, in particular, exhibit excellent stabilities and CO 2 adsorption properties. However, these frameworks display double-step adsorption behavior arising from steric repulsion between ammonium carbamates, which ultimately results in increased regeneration energies. Herein, we report frameworks of the type diamine-Mg 2 (olz) (olz 4- = ( E )-5,5'-(diazene-1,2-diyl)bis(2-oxidobenzoate)) that feature diverse diamines with bulky substituents and display desirable single-step CO 2 adsorption across a wide range of pressures and temperatures. Analysis of CO 2 adsorption data reveals that the basicity of the pore-dwelling amine─in addition to its steric bulk─is an important factor influencing adsorption step pressure; furthermore, the amine steric bulk is found to be inversely correlated with the degree of cooperativity in CO 2 uptake. One material, ee-2-Mg 2 (olz) (ee-2 = N , N -diethylethylenediamine), adsorbs >90% of the CO 2 from a simulated coal flue stream and exhibits exceptional thermal and oxidative stability over the course of extensive adsorption/desorption cycling, placing it among top-performing adsorbents to date for CO 2 capture from a coal flue gas. Spectroscopic characterization and van der Waals-corrected density functional theory calculations indicate that diamine-Mg 2 (olz) materials capture CO 2 via the formation of ammonium carbamate chains. These results point more broadly to the opportunity for fundamentally advancing materials in this class through judicious design.

Metal-organic frameworks (MOFs) are porous, crystalline solids constructed from organic linkers and inorganic nodes that have been widely studied for applications in gas storage, chemical separations, and drug delivery. Owing to their highly modular structures and tunable pore environments, we propose that MOFs have significant untapped potential as catalysts and reagents relevant to the synthesis of next-generation therapeutics. Herein, we outline the properties of MOFs that make them promising for applications in synthetic organic chemistry, including new reactivity and selectivity, enhanced robustness, and user-friendly preparation. In addition, we outline the challenges facing the field and propose new directions to maximize the utility of MOFs for drug synthesis. This perspective aims to bring together the organic and MOF communities to develop new heterogeneous platforms capable of achieving synthetic transformations that cannot be replicated by homogeneous systems.

Metal-organic frameworks (MOFs) are crystalline, porous solids constructed from organic linkers and inorganic nodes that are promising for applications in chemical separations, gas storage, and catalysis, among many others. However, a major roadblock to the widespread implementation of MOFs, including highly tunable and hydrolytically stable Zr- and Hf-based frameworks, is their benchtop-scalable synthesis, as MOFs are typically prepared under highly dilute (≤0.01 M) solvothermal conditions. This necessitates the use of liters of organic solvent to prepare only a few grams of MOF. Herein, we demonstrate that Zr- and Hf-based frameworks (eight examples) can self-assemble at much higher reaction concentrations than are typically utilized, up to 1.00 M in many cases. Combining stoichiometric amounts of Zr or Hf precursors with organic linkers at high concentrations yields highly crystalline and porous MOFs, as confirmed by powder X-ray diffraction (PXRD) and 77 K N 2 surface area measurements. Furthermore, the use of well-defined pivalate-capped cluster precursors avoids the formation of ordered defects and impurities that arise from standard metal chloride salts. These clusters also introduce pivalate defects that increase the exterior hydrophobicity of several MOFs, as confirmed by water contact angle measurements. Overall, our findings challenge the standard assumption that MOFs must be prepared under highly dilute solvothermal conditions for optimal results, paving the way for their scalable and user-friendly synthesis in the laboratory.

Emissive covalent organic frameworks (COFs) have recently emerged as next-generation porous materials with attractive properties such as tunable topology, porosity, and inherent photoluminescence. Among the different types of COFs, substoichiometric frameworks (so-called Type III COFs) are especially attractive due to the possibility of not only generating unusual topology and complex pore architectures but also facilitating the introduction of well-defined functional groups at precise locations for desired functions. Herein, the first example of a highly emissive (PLQY 6.8%) substoichiometric 2D-COF (COF-SMU-1) featuring free uncondensed aldehyde groups is reported. In particular, COF-SMU-1 features a dual-pore architecture with an overall bex net topology, tunable emission in various organic solvents, and distinct colorimetric changes in the presence of water. To gain further insights into its photoluminescence properties, the charge transfer, excimer emission, and excited state exciton dynamics of COF-SMU-1 are investigated using femtosecond transient absorption spectroscopy in different organic solvents. Additionally, highly enhanced atmospheric water-harvesting properties of COF-SMU-1 are revealed using FT-IR and water sorption studies.The findings will not only lead to in-depth understanding of structure-property relationships in emissive COFs but also open new opportunities for designing COFs for potential applications in solid-state lighting and water harvesting., (© 2022 Wiley-VCH GmbH.)

Metal-organic frameworks (MOFs) are porous, crystalline materials constructed from organic linkers and inorganic nodes with myriad potential applications in chemical separations, catalysis, and drug delivery. A major barrier to the application of MOFs is their poor scalability, as most frameworks are prepared under highly dilute solvothermal conditions using toxic organic solvents. Herein, we demonstrate that combining a range of linkers with low-melting metal halide (hydrate) salts leads directly to high-quality MOFs without added solvent. Frameworks prepared under these ionothermal conditions possess porosities comparable to those prepared under traditional solvothermal conditions. In addition, we report the ionothermal syntheses of two frameworks that cannot be prepared directly under solvothermal conditions. Overall, the user-friendly method reported herein should be broadly applicable to the discovery and synthesis of stable metal-organic materials., (© 2023 Wiley-VCH GmbH.)

The crystal packing of organic chromophores has a profound impact on their photophysical properties. Molecular crystal engineering is generally incapable of producing precisely spaced arrays of molecules for use in photovoltaics, light-emitting diodes, and sensors. A promising alternative strategy is the incorporation of chromophores into crystalline metal-organic frameworks (MOFs), leading to matrix coordination-induced emission (MCIE) upon confinement. However, it remains unclear how the precise arrangement of chromophores and defects dictates photophysical properties in these systems, limiting the rational design of well-defined photoluminescent materials. Herein, we report new, robust Zr-based MOFs constructed from the linker tetrakis(4-carboxyphenyl)ethylene (TCPE 4- ) that exhibit an unexpected structural transition in combination with a prominent shift from green to blue photoluminescence (PL) as a function of the amount of acid modulator (benzoic, formic, or acetic acid) used during synthesis. Time-resolved PL (TRPL) measurements provide full spectral information and reveal that the observed hypsochromic shift arises due to a higher concentration of linker substitution defects at higher modulator concentrations, leading to broader excitation transfer-induced spectral diffusion. Spectral diffusion of this type has not been reported in a MOF to date, and its observation provides structural information that is otherwise unobtainable using traditional crystallographic techniques. Our findings suggest that defects have a profound impact on the photophysical properties of MOFs and that their presence can be readily tuned to modify energy transfer processes within these materials.

Strategies for the sustainable synthesis of redox-active organic polymers could lead to next-generation organic electrode materials for electrochemical energy storage, electrocatalysis, and electro-swing chemical separations. Among redox-active moieties, benzils or aromatic 1,2-diones are particularly attractive due to their high theoretical gravimetric capacities and fast charge/discharge rates. Herein, we demonstrate that the cyanide-catalyzed polymerization of simple dialdehyde monomers unexpectedly leads to insoluble redox-active benzil-linked polymers instead of the expected benzoin polymers, as supported by solid-state nuclear magnetic resonance spectroscopy and electrochemical characterization. Mechanistic studies suggest that cyanide-mediated benzoin oxidation occurs by hydride transfer to the solvent, and that the insolubility of the benzil-linked polymers protects them from subsequent cyanolysis. The thiophene-based polymer poly(BTDA) is an intriguing organic electrode material that demonstrates two reversible one-electron reductions with monovalent cations such as Li + and Na + but one two-electron reduction with divalent Mg 2+ . As such, the tandem benzoin-oxidation polymerization reported herein represents a sustainable method for the synthesis of highly tunable and redox-active organic materials.

Chlorine (Cl 2 ) is a toxic and corrosive gas that is both an essential reagent in industry and a potent chemical warfare agent. Materials that can strongly bind Cl 2 at low pressures are essential for industrial and civilian personal protective equipment (PPE). Herein, we report the first examples of irreversible Cl 2 capture via the dichlorination of alkene linkages in Zr-based metal-organic frameworks. Frameworks constructed from fumarate (Zr-fum) and stilbene (Zr-stilbene) linkers retain long-range order and accessible porosity after alkene dichlorination. In addition, energy-dispersive X-ray spectroscopy reveals an even distribution of Cl throughout both materials after Cl 2 capture. Cl 2 uptake experiments reveal high irreversible uptake of Cl 2 (>10 wt %) at low partial pressures (<100 mbar), particularly in Zr-fum. In contrast, traditional porous carbons mostly display reversible Cl 2 capture, representing a continued risk to users after exposure. Overall, our results support that alkene dichlorination represents a new pathway for reactive Cl 2 capture, opening new opportunities for binding this gas irreversibly in PPE.

Metal-organic frameworks bearing coordinatively unsaturated Mg(II) sites are promising materials for gas storage, chemical separations, and drug delivery due to their low molecular weights and lack of toxicity. However, there remains a limited number of such MOFs reported in the literature. Herein, we investigate the gas sorption properties of the understudied framework Mg 2 ( m -dobdc) (dobdc 4- = 4,6-dioxido-1,3-benzenedicarboxylate) synthesized under both solvothermal and mechanochemical conditions. Both materials are found to be permanently porous, as confirmed by 77 K N 2 adsorption measurements. In particular, Mg 2 ( m -dobdc) synthesized under mechanochemical conditions using exogenous organic base displays one of the highest capacities reported to date (6.14 mmol/g) for CO 2 capture in a porous solid under simulated coal flue gas conditions (150 mbar, 40 °C). As such, mechanochemically synthesized Mg 2 ( m -dobdc) represents a promising new framework for applications requiring high gas adsorption capacities in a porous solid., Competing Interests: Conflicts of interest P.J.M. is listed as an inventor on several patents related to the application of MOFs for gas capture.

Carbon capture and sequestration (CCS) from industrial point sources and direct air capture are necessary to combat global climate change. A particular challenge faced by amine-based sorbents-the current leading technology-is poor stability towards O 2 . Here, we demonstrate that CO 2 chemisorption in γ-cylodextrin-based metal-organic frameworks (CD-MOFs) occurs via HCO 3 - formation at nucleophilic OH - sites within the framework pores, rather than via previously proposed pathways. The new framework KHCO 3 CD-MOF possesses rapid and high-capacity CO 2 uptake, good thermal, oxidative, and cycling stabilities, and selective CO 2 capture under mixed gas conditions. Because of its low cost and performance under realistic conditions, KHCO 3 CD-MOF is a promising new platform for CCS. More broadly, our work demonstrates that the encapsulation of reactive OH - sites within a porous framework represents a potentially general strategy for the design of oxidation-resistant adsorbents for CO 2 capture., (© 2022 Wiley-VCH GmbH.)

Organic electrode materials offer unique opportunities to utilize ion-electrode interactions to develop diverse, versatile, and high-performing secondary batteries, particularly for applications requiring high power densities. However, a lack of well-defined structure-property relationships for redox-active organic materials restricts the advancement of the field. Herein, we investigate a family of diimide-based polymer materials with several charge-compensating ions (Li + , Na + , K + ) in order to systematically probe how redox-active moiety, ion, and polymer flexibility dictate their thermodynamic and kinetic properties. When favorable ion-electrode interactions are employed ( e.g. , soft K + anions with soft perylenediimide dianions), the resulting batteries demonstrate increased working potentials and improved cycling stabilities. Further, for all polymers examined herein, we demonstrate that K + accesses the highest percentage of redox-active groups due to its small solvation shell/energy. Through crown ether experiments, cyclic voltammetry, and activation energy measurements, we provide insights into the charge compensation mechanisms of three different polymer structures and rationalize these findings in terms of the differing degrees of improvements observed when cycling with K + . Critically, we find that the most flexible polymer enables access to the highest fraction of active sites due to the small activation energy barrier during charge/discharge. These results suggest that improved capacities may be accessible by employing more flexible structures. Overall, our in-depth structure-activity investigation demonstrates how variables such as polymer structure and cation can be used to optimize battery performance and enable the realization of novel battery chemistries., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Acid modulation is among the most widely employed methods for preparing metal-organic frameworks (MOFs) that are both stable and highly crystalline, yet there exist few guiding principles for selecting the optimal modulator for a given system. Using the Zr-based MOFs UiO-66 and UiO-68-Me 2 (UiO = Universitetet i Oslo) as representative materials, here we present for the first time an in-depth structure-activity study of acid modulators and identify key principles of modulation for the synthesis of highly crystalline Zr-MOFs. By applying whole pattern fitting of powder X-ray diffraction (PXRD) patterns as a technique for evaluating modulator efficacy, complemented by scanning electron microscopy (SEM), 1 H NMR, and thermogravimetric analysis (TGA), we demonstrate that the key to effective modulation is competition between the linker and modulator for coordination to the Zr secondary building units (SBUs). Specifically, we illustrate that a close match in p K a and structure between the linker and modulator favors larger and more well-defined crystallites, particularly with sterically unhindered aromatic acid modulators. Based on our findings, we demonstrate that 5-membered heteroaromatic carboxylic acids are among the most efficient acid modulators identified to date for the synthesis of several representative Zr-MOFs with fcu net topologies. In addition, we find that coordination modulation is superior to exogenous acid modulation at higher modulator concentrations. Finally, we compare 1 H NMR and TGA as data-driven methods for quantifying linker deficiencies in modulated MOF syntheses. The guiding principles established herein have critical implications for the scalable and controllable synthesis of highly crystalline and stable MOFs relevant to chemical separations, gas storage, and catalysis.

Carbon capture at fossil fuel-fired power plants is a critical strategy to mitigate anthropogenic contributions to global warming, but widespread deployment of this technology is hindered by a lack of energy-efficient materials that can be optimized for CO 2 capture from a specific flue gas. As a result of their tunable, step-shaped CO 2 adsorption profiles, diamine-functionalized metal-organic frameworks (MOFs) of the form diamine-Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are among the most promising materials for carbon capture applications. Here, we present a detailed investigation of dmen-Mg 2 (dobpdc) (dmen = 1,2-diamino-2-methylpropane), one of only two MOFs with an adsorption step near the optimal pressure for CO 2 capture from coal flue gas. While prior characterization suggested that this material only adsorbs CO 2 to half capacity (0.5 CO 2 per diamine) at 1 bar, we show that the half-capacity state is actually a metastable intermediate. Under appropriate conditions, the MOF adsorbs CO 2 to full capacity, but conversion from the half-capacity structure happens on a very slow time scale, rendering it inaccessible in traditional adsorption measurements. Data from solid-state magic angle spinning nuclear magnetic resonance spectroscopy, coupled with van der Waals-corrected density functional theory, indicate that ammonium carbamate chains formed at half capacity and full capacity adopt opposing configurations, and the need to convert between these states likely dictates the sluggish post-half-capacity uptake. By use of the more symmetric parent framework Mg 2 (pc-dobpdc) (pc-dobpdc 4- = 3,3'-dioxidobiphenyl-4,4'-dicarboxylate), the metastable trap can be avoided and the full CO 2 capacity of dmen-Mg 2 (pc-dobpdc) accessed under conditions relevant for carbon capture from coal-fired power plants.

The controlled introduction of defects into MOFs is a powerful strategy to induce new physiochemical properties and improve their performance for target applications. Herein, we present a new strategy for defect formation and amorphization of the canonical MOF-74 frameworks based on fine-tuning of adsorbate-framework interactions in the metal congener, hence introducing structural defects. Specifically, we demonstrate that controlled interactions between the MOF and bidentate ligands adsorbed in the pores initiates defect formation and eventual amorphization of the crystal. These structural features unlock properties that are otherwise absent in the ordered framework, such as broad-band fluorescence. The ability to introduce defects by adsorbate-framework interactions, coupled with the inherent tunability and modularity of these structures, provides a new route for the synthesis of diverse heterogeneous and hybrid materials., Competing Interests: Conflicts of interest A.R.L. discloses a financial stake in BioLum Sciences, LLC, a company developing medical devices. P.J.M is listed as an inventor on several provisional patents involving functionalized variants of MOF-74.

Hydrogen sulfide (H 2 S) is an endogenous gasotransmitter with potential therapeutic value for treating a range of disorders, such as ischemia-reperfusion injury resulting from a myocardial infarction or stroke. However, the medicinal delivery of H 2 S is hindered by its corrosive and toxic nature. In addition, small molecule H 2 S donors often generate other reactive and sulfur-containing species upon H 2 S release, leading to unwanted side effects. Here, we demonstrate that H 2 S release from biocompatible porous solids, namely metal-organic frameworks (MOFs), is a promising alternative strategy for H 2 S delivery under physiologically relevant conditions. In particular, through gas adsorption measurements and density functional theory calculations we establish that H 2 S binds strongly and reversibly within the tetrahedral pockets of the fumaric acid-derived framework MOF-801 and the mesaconic acid-derived framework Zr-mes, as well as the new itaconic acid-derived framework CORN-MOF-2. These features make all three frameworks among the best materials identified to date for the capture, storage, and delivery of H 2 S. In addition, these frameworks are non-toxic to HeLa cells and capable of releasing H 2 S under aqueous conditions, as confirmed by fluorescence assays. Last, a cellular ischemia-reperfusion injury model using H9c2 rat cardiomyoblast cells corroborates that H 2 S-loaded MOF-801 is capable of mitigating hypoxia-reoxygenation injury, likely due to the release of H 2 S. Overall, our findings suggest that H 2 S-loaded MOFs represent a new family of easily-handled solid sources of H 2 S that merit further investigation as therapeutic agents. In addition, our findings add Zr-mes and CORN-MOF-2 to the growing lexicon of biocompatible MOFs suitable for drug delivery., Competing Interests: P. J. M. is listed as a co-inventor on several patents that include functionalized metal–organic frameworks., (This journal is © The Royal Society of Chemistry.)

Metal-organic frameworks (MOFs) are emerging as sustainable reagents and catalysts with promising applications in synthetic chemistry. Although the hydrothermal stabilities of MOFs have been well studied, their robustness toward various reagents, including acids, bases, nucleophiles, electrophiles, oxidants, and reductants, remains poorly characterized. As such, heterogeneous platforms for promising catalysts are generally identified on an ad hoc basis and have largely been limited to carboxylate frameworks to date. To address these limitations, here we systematically characterize the robustness of 17 representative carboxylate, salicylate, and azolate MOFs toward 30 conditions representing the scope of synthetic organic chemistry. Specifically, analysis of the full width at half-maximum of powder X-ray diffraction patterns, as well as infrared spectroscopy, 77 K N 2 adsorption measurements, and scanning electron microscopy in select cases are employed to appraise framework degradation and dissolution under a range of representative conditions. Our studies demonstrate that azolate MOFs, such as Fe 2 (bdp) 3 (bdp 2- = 4,4'-(1,4-phenylene)bis(pyrazolate)), generally possess excellent chemical stabilities under myriad conditions. In addition, we find that carboxylate and salicylate frameworks possess complementary stabilities, with carboxylate MOFs possessing superior robustness toward acids, electrophiles, and oxidants, and salicylate MOFs demonstrating improved robustness toward bases, nucleophiles, and reductants. The guidelines provided herein should facilitate the rational design of robust frameworks for applications in synthetic chemistry and guide the development of new strategies for the postsynthetic modification of MOFs as well.

Fluoroarenes are widely used in medicinal, agricultural, and materials chemistry, and yet their production remains a critical challenge in organic synthesis. Indeed, the nearly identical physical properties of these vital building blocks hinders their purification by traditional methods, such as flash chromatography or distillation. As a result, the Balz-Schiemann reaction is currently employed to prepare fluoroarenes instead of more atom-economical C-H fluorination reactions, which produce inseparable mixtures of regioisomers. Herein, we propose an alternative solution to this problem: the purification of mixtures of fluoroarenes using metal-organic frameworks (MOFs). Specifically, we demonstrate that controlling the interaction of fluoroarenes with adjacent coordinatively unsaturated Mg 2+ centers within a MOF enables the separation of fluoroarene mixtures with unparalleled selectivities. Liquid-phase multicomponent equilibrium adsorption data and breakthrough measurements coupled with van der Waals-corrected density functional theory calculations reveal that the materials Mg 2 (dobdc) (dobdc 4- = 2,5-dioxidobenzene-1,4-dicarboxylate) and Mg 2 ( m -dobdc) ( m -dobdc 4- = 2,4-dioxidobenzene-1,5-dicarboxylate) are capable of separating the difluorobenzene isomers from one another. Additionally, these frameworks facilitate the separations of fluoroanisoles, fluorotoluenes, and fluorochlorobenzenes. In addition to enabling currently unfeasible separations for the production of fluoroarenes, our results suggest that carefully controlling the interaction of isomers with not one but two strong binding sites within a MOF provides a general strategy for achieving challenging liquid-phase separations.

Small-molecule impurities, such as N -nitrosodimethylamine (NDMA), have infiltrated the generic drug industry, leading to recalls in commonly prescribed blood pressure and stomach drugs in over 43 countries since 2018 and directly affecting tens of millions of patients. One promising strategy to remove small-molecule impurities like NDMA from drug molecules is by size exclusion, in which the contaminant is removed by selective adsorption onto a (micro)porous material due to its smaller size. However, current solution-phase size-exclusion separations are primarily limited by the throughput-selectivity trade-off. Here, we report a bioinspired solution to conquer these critical challenges by leveraging the assembly of atomically precise building blocks into hierarchically porous structures. We introduce a bottom-up approach to form micropores, mesopores, and macroscopic superstructures simultaneously using functionalized oxozirconium clusters as building blocks. Further, we leverage recent advances in photopolymerization to design macroscopic flow structures to mitigate backpressure. Based on these multiscale design principles, we engineer simple, inexpensive devices that are able to separate NDMA from contaminated drugs. Beyond this urgent model system, we expect this design strategy to open up hitherto unexplored avenues of nanomaterial superstructure fabrication for a range of size-exclusion purification strategies.

Carbon capture and sequestration is necessary to tackle one of the biggest problems facing society: global climate change resulting from anthropogenic carbon dioxide (CO 2 ) emissions. Despite this pressing need, we still rely on century-old technology-aqueous amine scrubbers-to selectively remove CO 2 from emission streams. Amine scrubbers are effective due to their exquisite chemoselectivity towards CO 2 to form ammonium carbamates and (bi)carbonates, but suffer from several unavoidable limitations. In this perspective, we highlight the need for CO 2 capture via new chemistry that goes beyond the traditional formation of ammonium carbamates. In particular, we demonstrate how ionic liquid and metal-organic framework sorbents can give rise to capture products that are not favourable for aqueous amines, including carbamic acids, carbamate-carbamic acid adducts, metal bicarbonates, alkyl carbonates, and carbonic acids. These new CO 2 binding modes may offer advantages including higher sorption capacities and lower regeneration energies, though additional research is needed to fully explore their utility for practical applications. Overall, we outline the unique challenges and opportunities involved in engineering new CO 2 capture chemistry into next-generation technologies., Competing Interests: The authors declare the following competing interest: P. J. M. is listed as an inventor on several patents related to the preparation of metal–organic frameworks for CO2 capture., (This journal is © The Royal Society of Chemistry.)

Metal-organic frameworks (MOFs) bearing coordinatively unsaturated metal centers, exemplified by the MOF-74 family of frameworks, are promising for applications ranging from gas separations and storage to Lewis acid catalysis. However, the scalable synthesis of MOF-74 analogues remains a significant challenge. Recently, mechanochemistry has emerged as a sustainable strategy for the preparation of MOFs in the solid state with minimal solvent waste. Mechanochemical methods typically rely on metal salts bearing basic anions to deprotonate the conjugate acid of the organic linker and a small amount of organic solvent or water to facilitate liquid assisted grinding. Here, we demonstrate that the liquid exogenous organic base Hünig's base (N,N-diisopropylethylamine) can fulfill both roles, enabling the mechanochemical synthesis of M2(dobdc) analogues (M = Mg, Mn, Co, Ni, Cu, Zn; dobdc4- = 2,5-dioxidobenzene-1,4-dicarboxylate) using metal nitrate salts in only 5 minutes at room temperature. Importantly, we demonstrate that this straightforward method can be generalized to prepare the isomeric framework Mg2(m-dobdc) (m-dobdc4- = 2,4-dioxidobenzene-1,5-dicarboxylate) and the expanded framework Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) under solvent-free conditions for the first time. The MOFs prepared using this method possess high crystallinities and surface areas, with the Mg2(m-dobdc) prepared herein representing the first reported permanently porous variant of this framework. This new sustainable mechanochemical synthesis of MOF-74 analogues should enable their preparation on a large scale for industrial applications.

A series of structurally diverse alcoholamine- and alkoxyalkylamine-functionalized variants of the metal-organic framework Mg 2 (dobpdc) are shown to adsorb CO 2 selectively via cooperative chain-forming mechanisms. Solid-state NMR spectra and optimized structures obtained from van der Waals-corrected density functional theory calculations indicate that the adsorption profiles can be attributed to the formation of carbamic acid or ammonium carbamate chains that are stabilized by hydrogen bonding interactions within the framework pores. These findings significantly expand the scope of chemical functionalities that can be utilized to design cooperative CO 2 adsorbents, providing further means of optimizing these powerful materials for energy-efficient CO 2 separations., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Natural gas has become the dominant source of electricity in the United States, and technologies capable of efficiently removing carbon dioxide (CO 2 ) from the flue emissions of natural gas-fired power plants could reduce their carbon intensity. However, given the low partial pressure of CO 2 in the flue stream, separation of CO 2 is particularly challenging. Taking inspiration from the crystal structures of diamine-appended metal-organic frameworks exhibiting two-step cooperative CO 2 adsorption, we report a family of robust tetraamine-functionalized frameworks that retain cooperativity, leading to the potential for exceptional efficiency in capturing CO 2 under the extreme conditions relevant to natural gas flue emissions. The ordered, multimetal coordination of the tetraamines imparts the materials with extraordinary stability to adsorption-desorption cycling with simulated humid flue gas and enables regeneration using low-temperature steam in lieu of costly pressure or temperature swings., (Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

Carbon capture and sequestration is a key element of global initiatives to minimize anthropogenic greenhouse gas emissions. Although many investigations of new candidate CO 2 capture materials focus on equilibrium adsorption properties, it is also critical to consider adsorption/desorption kinetics when evaluating adsorbent performance. Diamine-appended variants of the metal-organic framework Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are promising materials for CO 2 capture because of their cooperative chemisorption mechanism and associated step-shaped equilibrium isotherms, which enable large working capacities to be accessed with small temperature swings. However, the adsorption/desorption kinetics of these unique materials remain understudied. More generally, despite the necessity of kinetics characterization to advance adsorbents toward commercial separations, detailed kinetic studies of metal-organic framework-based gas separations remain rare. Here, we systematically investigate the CO 2 adsorption kinetics of diamine-appended Mg 2 (dobpdc) variants using a thermogravimetric analysis (TGA) assay. In particular, we examine the effects of diamine structure, temperature, and partial pressure on CO 2 adsorption and desorption kinetics. Importantly, most diamine-appended Mg 2 (dobpdc) variants exhibit an induction period prior to reaching the maximum rate of CO 2 adsorption, which we attribute to their unique cooperative chemisorption mechanism. In addition, these materials exhibit inverse Arrhenius behavior, displaying faster adsorption kinetics and shorter induction periods at lower temperatures. Using the Avrami model for nucleation and growth kinetics, we determine rate constants for CO 2 adsorption and quantitatively compare rate constants among different diamine-appended variants. Overall, these results provide guidelines for optimizing adsorbent design to facilitate CO 2 capture from diverse target streams and highlight kinetic phenomena relevant for other materials in which cooperative chemisorption mechanisms are operative., Competing Interests: The authors declare the following competing financial interest: J. R. L. has a financial interest in Mosaic Materials, Inc., a start-up company working to commercialize metal–organic frameworks for gas separations, including CO2 capture applications. The University of California, Berkeley has applied for a patent on some of the materials discussed herein, on which J. R. L., P. J. M., and R. L. S. are listed as inventors., (This journal is © The Royal Society of Chemistry.)

Variable-temperature 15 N solid-state NMR spectroscopy is used to uncover the dynamics of three diamines appended to the metal-organic framework Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate), an important family of CO 2 capture materials. The results imply both bound and free amine nitrogen environments exist when diamines are coordinated to the framework open Mg 2+ sites. There are rapid exchanges between two nitrogen environments for all three diamines, the rates and energetics of which are quantified by 15 N solid-state NMR data and corroborated by density functional theory calculations and molecular dynamics simulations. The activation energy for the exchange provides a measure of the metal-amine bond strength. The unexpected negative correlation between the metal-amine bond strength and CO 2 adsorption step pressure reveals that metal-amine bond strength is not the only important factor in determining the CO 2 adsorption properties of diamine-appended Mg 2 (dobpdc) metal-organic frameworks.

Leveraging molecular-level controls to enhance CO 2 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(BH 4 ) 2 nanocrystals and reduced graphene oxide (MBHg) is described. These nanomaterials exhibit kinetically controlled, irreversible CO 2 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 CO 2 and MBHg and unveil the role of chemically activated, metastable (BH 3 -HCOO) - centers that display more thermodynamically favorable reaction and potentially faster reaction kinetics than the parent BH 4 - centers. Overall, it is demonstrated that size reduction to the nanoscale regime and the generation of reactive, metastable intermediates improve the CO 2 uptake properties in metal borohydride nanomaterials., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Supported by increasingly available reserves, natural gas is achieving greater adoption as a cleaner-burning alternative to coal in the power sector. As a result, carbon capture and sequestration from natural gas-fired power plants is an attractive strategy to mitigate global anthropogenic CO 2 emissions. However, the separation of CO 2 from other components in the flue streams of gas-fired power plants is particularly challenging due to the low CO 2 partial pressure (∼40 mbar), which necessitates that candidate separation materials bind CO 2 strongly at low partial pressures (≤4 mbar) to capture ≥90% of the emitted CO 2 . High partial pressures of O 2 (120 mbar) and water (80 mbar) in these flue streams have also presented significant barriers to the deployment of new technologies for CO 2 capture from gas-fired power plants. Here, we demonstrate that functionalization of the metal-organic framework Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) with the cyclic diamine 2-(aminomethyl)piperidine (2-ampd) produces an adsorbent that is capable of ≥90% CO 2 capture from a humid natural gas flue emission stream, as confirmed by breakthrough measurements. This material captures CO 2 by a cooperative mechanism that enables access to a large CO 2 cycling capacity with a small temperature swing (2.4 mmol CO 2 /g with Δ T = 100 °C). Significantly, multicomponent adsorption experiments, infrared spectroscopy, magic angle spinning solid-state NMR spectroscopy, and van der Waals-corrected density functional theory studies suggest that water enhances CO 2 capture in 2-ampd-Mg 2 (dobpdc) through hydrogen-bonding interactions with the carbamate groups of the ammonium carbamate chains formed upon CO 2 adsorption, thereby increasing the thermodynamic driving force for CO 2 binding. In light of the exceptional thermal and oxidative stability of 2-ampd-Mg 2 (dobpdc), its high CO 2 adsorption capacity, and its high CO 2 capture rate from a simulated natural gas flue emission stream, this material is one of the most promising adsorbents to date for this important separation.

In recent years, the power sector has shown a growing reliance on natural gas, a cleaner-burning fuel than coal that emits approximately half as much CO 2 per kWh of energy produced. This rapid growth in the consumption of natural gas has led to increased CO 2 emissions from gas-fired power plants. To limit the contribution of fossil fuel combustion to atmospheric CO 2 levels, carbon capture and sequestration has been proposed as a potential emission mitigation strategy. However, despite extensive exploration of solid adsorbents for CO 2 capture, few studies have examined the performance of adsorbents in post-combustion capture processes specific to natural gas flue emissions. In this perspective, we emphasize the importance of considering gas-fired power plants alongside coal-fired plants in future analyses of carbon capture materials. We address specific challenges and opportunities related to adsorptive carbon capture from the emissions of gas-fired plants and discuss several promising candidate materials. Finally, we suggest experiments to determine the viability of new CO 2 capture materials for this separation. This broadening in the scope of current carbon capture research is urgently needed to accelerate the deployment of transformational carbon capture technologies., Competing Interests: Conflicts of interest The authors declare the following competing financial interests: J.R.L. has a financial interest in Mosaic Materials, Inc., a start-up company working to commercialize metal–organic frameworks for gas separations, including CO2 capture applications.

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-M 2 (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 CO 2 uptake in these materials. Here we leverage the crystallinity and tunability of this class of frameworks to perform a comprehensive study of CO 2 chemisorption. Using multinuclear nuclear magnetic resonance (NMR) spectroscopy experiments and van-der-Waals-corrected density functional theory (DFT) calculations for 13 diamine-M 2 (dobpdc) variants, we demonstrate that the canonical CO 2 chemisorption products, ammonium carbamate chains and carbamic acid pairs, can be readily distinguished and that ammonium carbamate chain formation dominates for diamine-Mg 2 (dobpdc) materials. In addition, we elucidate a new chemisorption mechanism in the material dmpn-Mg 2 (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 CO 2 uptake in diamine-M 2 (dobpdc) materials. Overall, our combined NMR and DFT approach enables a thorough depiction and understanding of CO 2 adsorption within diamine-M 2 (dobpdc) compounds, which may aid similar studies in other amine-functionalized adsorbents in the future.

Over one million tons of CS 2 are produced annually, and emissions of this volatile and toxic liquid, known to generate acid rain, remain poorly controlled. As such, materials capable of reversibly capturing this commodity chemical in an energy-efficient manner are of interest. Recently, we detailed diamine-appended metal-organic frameworks capable of selectively capturing CO 2 through a cooperative insertion mechanism that promotes efficient adsorption-desorption cycling. We therefore sought to explore the ability of these materials to capture CS 2 through a similar mechanism. Employing crystallography, spectroscopy, and gas adsorption analysis, we demonstrate that CS 2 is indeed cooperatively adsorbed in N,N-dimethylethylenediamine-appended M 2 (dobpdc) (M = Mg, Mn, Zn; dobpdc 4-  = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate), via the formation of electrostatically paired ammonium dithiocarbamate chains. In the weakly thiophilic Mg congener, chemisorption is cleanly reversible with mild thermal input. This work demonstrates that the cooperative insertion mechanism can be generalized to other high-impact target molecules.