Tetrameric self-assembling of water-lean solvents enables carbamate anhydride-based CO2 capture chemistry.

Carbon capture, utilization and storage is a key yet cost-intensive technology for the fight against climate change. Single-component water-lean solvents have emerged as promising materials for post-combustion CO2 capture, but little is known regarding their mechanism of action. Here we present a combined experimental and modelling study of single-component water-lean solvents, and we find that CO2 capture is accompanied by the self-assembly of reverse-micelle-like tetrameric clusters in solution. This spontaneous aggregation leads to stepwise cooperative capture phenomena with highly contrasting mechanistic and thermodynamic features. The emergence of well-defined supramolecular architectures displaying a hydrogen-bonded internal core, reminiscent of enzymatic active sites, enables the formation of CO2-containing molecular species such as carbamic acid, carbamic anhydride and alkoxy carbamic anhydrides. This system extends the scope of adducts and mechanisms observed during carbon capture. It opens the way to materials with a higher CO2 storage capacity and provides a means for carbamates to potentially act as initiators for future oligomerization or polymerization of CO2.

Chloride and Hydride Transfer as Keys to Catalytic Upcycling of Polyethylene into Liquid Alkanes.

Transforming polyolefin waste into liquid alkanes through tandem cracking-alkylation reactions catalyzed by Lewis-acid chlorides offers an efficient route for single-step plastic upcycling. Lewis acids in dichloromethane establish a polar environment that stabilizes carbenium ion intermediates and catalyzes hydride transfer, enabling breaking of polyethylene C-C bonds and forming C-C bonds in alkylation. Here, we show that efficient and selective deconstruction of low-density polyethylene (LDPE) to liquid alkanes is achieved with anhydrous aluminum chloride (AlCl3) and gallium chloride (GaCl3). Already at 60 °C, complete LDPE conversion was achieved, while maintaining the selectivity for gasoline-range liquid alkanes over 70 %. AlCl3 showed an exceptional conversion rate of 5000 g L D P E m o l c a t - 1 h - 1 ${{{\rm g}}_{{\rm L}{\rm D}{\rm P}{\rm E}}{{\rm \ }{\rm m}{\rm o}{\rm l}}_{{\rm c}{\rm a}{\rm t}}^{-1}{{\rm \ }{\rm h}}^{-1}}$ , surpassing other Lewis acid catalysts by two orders of magnitude. Through kinetic and mechanistic studies, we show that the rates of LDPE conversion do not correlate directly with the intrinsic strength of the Lewis acids or steric constraints that may limit the polymer to access the Lewis acid sites. Instead, the rates for the tandem processes of cracking and alkylation are primarily governed by the rates of initiation of carbenium ions and the subsequent intermolecular hydride transfer. Both jointly control the relative rates of cracking and alkylation, thereby determining the overall conversion and selectivity.

Proton Relay for the Rate Enhancement of Electrochemical Hydrogen Reactions at Heterogeneous Interfaces.

Proton transfer is critically important to many electrocatalytic reactions, and directed proton delivery could open new avenues for the design of electrocatalysts. However, although this approach has been successful in molecular electrocatalysis, proton transfer has not received the same attention in heterogeneous electrocatalyst design. Here, we report that a metal oxide proton relay can be built within heterogeneous electrocatalyst architectures and improves the kinetics of electrochemical hydrogen evolution and oxidation reactions. The volcano-type relationship between activity enhancement and pKa of amine additives confirms this improvement; we observe maximum rate enhancement when the pKa of a proton relay matches the pH of the electrolyte solution. Density-functional-theory-based reactivity studies reveal a decreased proton transfer energy barrier with a metal oxide proton relay. These findings demonstrate the possibility of controlling the proton delivery and enhancing the reaction kinetics by tuning the chemical properties and structures at heterogeneous interfaces.

Tuning aminopolycarboxylate chelators for efficient complexation of trivalent actinides.

The complexation of trivalent lanthanides and minor actinides (Am3+, Cm3+, and Cf3+) by the acyclic aminopolycarboxylate chelators 6,6'-((ethane-1,2-diylbis-((carboxymethyl)azanediyl))bis-(methylene))dipicolinic acid (H4octapa) and 6,6'-((((4-(1-(2-(2-(2-hydroxyethoxy)ethoxy)ethyl)-1H-1,2,3-triazol-4-yl)pyridine-2,6-diyl)bis-(methylene))bis-((carboxymethyl)azanediyl))bis-(methylene)) dipicolinic acid (H4pypa-peg) were studied using potentiometry, spectroscopy, competitive complexation liquid-liquid extraction, and ab initio molecular dynamics simulations. Two studied reagents are strong multidentate chelators, well-suited for applications seeking radiometal coordination for in-vivo delivery and f-element isolation. The previously reported H4octapa forms a compact coordination packet, while H4pypa-peg is less sterically constrained due to the presence of central pyridine ring. The solubility of H4octapa is limited in a non-complexing high ionic strength perchlorate media. However, the introduction of a polyethylene glycol group in H4pypa-peg increased the solubility without influencing its ability to complex the lanthanides and minor actinides in solution.

Theoretical Investigation of Single-Molecule-Magnet Behavior in Mononuclear Dysprosium and Californium Complexes.

Early-actinide-based (U, Np, and Pu) single-molecule magnets (SMMs) have yet to show magnetic properties similar to those of highly anisotropic lanthanide-based ones. However, there are not many studies exploring the late-actinides (more than half-filled f shells) as potential candidates for SMM applications. We computationally explored the electronic structure and magnetic properties of a hypothetical Cf(III) complex isostructural to the experimentally synthesized Dy(dbm)3(bpy) complex (bpy = 2,2'-bipyridine; dbm = dibenzoylmethanoate) via multireference methods and compared them to those of the Dy(III) analogue. This study shows that the Cf(III) complex can behave as a SMM and has a greater magnetic susceptibility compared to other experimentally and computationally studied early-actinide-based (U, Np, and Pu) magnetic complexes. However, Cf spontaneously undergoes α-decay and converts to Cm. Thus, we also explored the isostructural Cm(III)-based complex. The computed magnetic susceptibility and g-tensor values show that the Cm(III) complex has poor SMM behavior in comparison to both the Dy(III) and Cf(III) complexes, suggesting that the performance of Cf(III)-based magnets may be affected by α-decay and can explain the poor performance of experimentally studied Cf(III)-based molecular magnets in the literature. Further, this study suggests that the ligand field is dominant in Cf(III), which helps to increase the magnetization blocking barrier by nearly 3 times that of its 4f congener.

Supramolecular Recognition within a Nanosized "Buckytrap" That Exhibits Substantial Photoconductivity.

We report here a nanosized "buckytrap", 1, constructed from two bis-zinc(II) expanded-TTF (exTTF) porphyrin subunits. Two forms, 1a and 1b, differing in the axial ligands, H2O vs tetrahydrofuran (THF), were isolated and characterized. Discrete host-guest inclusion complexes are formed upon treatment with fullerenes as inferred from a single-crystal X-ray structural analyses of 1a with C70. The fullerene is found to be encapsulated within the inner pseudohexagonal cavity of 1a. In contrast, the corresponding free-base derivative (2) was found to form infinite ball-and-socket type supramolecular organic frameworks (3D-SOFs) with fullerenes, (2•C60)n or (2•C70)n. This difference is ascribed to the fact that in 1a and 1b the axial positions are blocked by a H2O or THF ligand. Emission spectroscopic studies supported a 1:1 host-guest binding stoichiometry, allowing association constants of (2.0 ± 0.5) × 104 M-1 and (4.3 ± 0.9) × 104 M-1 to be calculated for C60 and C70, respectively. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) studies of solid films of the Zn-complex 1a revealed that the intrinsic charge carrier transport, i.e., pseudo-photoconductivity (ϕ∑µ), increases upon fullerene inclusion (e.g., ϕ∑µ = 1.53 × 10-4 cm2 V-1 s-1 for C60⊂(1a)2 and ϕ∑µ = 1.45 × 10-4 cm2 V-1 s-1 for C70⊂(1a)2 vs ϕ∑µ = 2.49 × 10-5 cm2 V-1 s-1 for 1a) at 298 K. These findings provide support for the notion that controlling the nature of self-assembly supramolecular constructs formed from exTTF-porphyrin dimers through metalation or choice of fullerene can be used to regulate key functional features, including photoconductivity.

Photocatalytic Biocidal Coatings Featuring Zr6Ti4-Based Metal-Organic Frameworks.

The world is currently suffering socially, economically, and politically from the recent pandemic outbreak due to the coronavirus disease 2019 (COVID-19), and those in hospitals, schools, and elderly nursing homes face enhanced threats. Healthcare textiles, such as masks and medical staff gowns, are susceptible to contamination of various pathogenic microorganisms, including bacteria and viruses. Metal-organic frameworks (MOFs) can potentially address these challenges due to their tunable reactivity and ability to be incorporated as porous coatings on textile materials. Here, we report how incorporating titanium into the zirconium-pyrene-based MOF NU-1000, denoted as NU-1012, generates a highly reactive biocidal photocatalyst. This MOF features a rare ligand migration phenomenon, and both the Ti/Zr center and the pyrene linker act synergistically as dual active centers and widen the absorption band for this material, which results in enhanced reactive oxygen species generation upon visible light irradiation. Additionally, we found that the ligand migration process is generally applicable to other csq topology Zr-MOFs. Importantly, NU-1012 can be easily incorporated onto cotton textile cloths as a coating, and the resulting composite material demonstrates fast and potent biocidal activity against Gram-negative bacteria (Escherichia coli), Gram-positive bacteria (Staphylococcus epidermidis), and T7 bacteriophage virus with up to a 7-log(99.99999%) reduction within 1 h under simulated daylight.

Leveraging Nitrogen Linkages in the Formation of a Porous Thorium-Organic Nanotube Suitable for Iodine Capture.

We report the synthesis, characterization, and iodine capture application of a novel thorium-organic nanotube, TSN-626, [Th6O4(OH)4(C6H4NO2)7(CHO2)5(H2O)3]·3H2O. The classification as a metal-organic nanotube (MONT) distinguishes it as a rare and reduced dimensionality subset of metal-organic frameworks (MOFs); the structure is additionally hallmarked by low node connectivity. TSN-626 is composed of hexameric thorium secondary building units and mixed O/N-donor isonicotinate ligands that demonstrate selective ditopicity, yielding both terminating and bridging moieties. Because hard Lewis acid tetravalent metals have a propensity to bind with electron donors of rival hardness (e.g., carboxylate groups), such Th-N coordination in a MOF is uncommon. However, the formation of key structural Th-N bonds in TSN-626 cap some of the square antiprismatic metal centers, a position usually occupied by terminal water ligands. TSN-626 was characterized by using complementary analytical and computational techniques: X-ray diffraction, vibrational spectroscopy, N2 physisorption isotherms, and density functional theory. TSN-626 satisfies design aspects for the chemisorption of iodine. The synergy between accessibility through pores, vacancies at the metal-oxo nodes, and pendent N-donor sites allowed a saturated iodine loading of 955 mg g-1 by vapor methods. The crystallization of TSN-626 diversifies actinide-MOF linker selection to include soft electron donors, and these Th-N linkages can be leveraged for the investigation of metal-to-ligand bonding and unconventional topological expressions.

Electron transitions in a Ce(III)-catecholate metal-organic framework.

A rare three-dimensional catecholate-based Ce(III) metal-organic framework (MOF), denoted as NU-1701, has been synthesized and crystallographically characterized. Density functional theory calculations highlight various possible electronic transitions that may present in NU-1701. These transitions are competitive and indicate increased lanthanide character of Ce(III).

Unsaturated Sulfur Crown Ethers Can Extract Mercury(II) and Show Promise for Future Copernicium(II) Studies: A Combined Experimental and Computational Study.

The unsaturated hexathia-18-crown-6 (UHT18C6) molecule was investigated for the extraction of Hg(II) in HCl and HNO3 media. This extractant can be directly compared to the recently studied saturated hexathia-18-crown-6 (HT18C6). The default conformation of the S lone pairs in UHT18C6 is endodentate, where the pocket of the charge density, according to the crystal structures, is oriented toward the center of the ring, which should allow better extraction for Hg(II) compared to the exodentate HT18C6. Batch study experiments showed that Hg(II) had better extraction at low acid molarity (ca. 99% in HCl and ca. 95% in HNO3), while almost no extraction was observed above 0.4 M HCl and 4 M HNO3 (<5%). Speciation studies were conducted with the goal of delineating a plausible extraction mechanism. Density functional theory calculations including relativistic effects were carried out on both Hg(II)-encapsulated HT18C6 and UHT18C6 complexes to shed light on the binding strength and the nature of bonding. Our calculations offer insights into the extraction mechanism. In addition to Hg(II), calculations were performed on the hypothetical divalent Cn(II) ion, and showed that HT18C6 and UHT18C6 could extract Cn(II). Finally, the extraction kinetics were explored to assess whether this crown can extract the short-lived Cn(II) species in a future online experiment.

Using Redox-Active Ligands to Generate Actinide Ligand Radical Species.

Using a redox-active dioxophenoxazine ligand, DOPO (DOPO = 2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazine-9-olate), a family of actinide (U, Th, Np, and Pu) and Hf tris(ligand) coordination compounds was synthesized. The full characterization of these species using 1H NMR spectroscopy, electronic absorption spectroscopy, SQUID magnetometry, and X-ray crystallography showed that these compounds are analogous and exist in the form M(DOPOq)2(DOPOsq), where two ligands are of the oxidized quinone form (DOPOq) and the third is of the reduced semiquinone (DOPOsq) form. The electronic structures of these complexes were further investigated using CASSCF calculations, which revealed electronic structures consistent with metals in the +4 formal oxidation state and one unpaired electron localized on one ligand in each complex. Furthermore, f orbitals of the early actinides show a sizable bonding overlap with the ligand 2p orbitals. Notably, this is the first example of a plutonium-ligand radical species and a rare example of magnetic data being recorded for a homogeneous plutonium coordination complex.

Cu[Ni(2,3-pyrazinedithiolate)2] Metal-Organic Framework for Electrocatalytic Hydrogen Evolution.

The application of metal-organic frameworks (MOFs) as electrocatalysts for small molecule activation has been an emerging topic of research. Previous studies have suggested that two-dimensional (2D) dithiolene-based MOFs are among the most active for the hydrogen evolution reaction (HER). Here, a three-dimensional (3D) dithiolene-based MOF, Cu[Ni(2,3-pyrazinedithiolate)2] (1), is evaluated as an electrocatalyst for the HER. In pH 1.3 aqueous electrolyte solution, 1 exhibits a catalytic onset at -0.43 V vs the reversible hydrogen electrode (RHE), an overpotential (η10 mA/cm2) of 0.53 V to reach a current density of 10 mA/cm2, and a Tafel slope of 69.0 mV/dec. Interestingly, under controlled potential electrolysis, 1 undergoes an activation process that results in a more active catalyst with a 200 mV reduction in the catalytic onset and η10 mA/cm2. It is proposed that the activation process is a result of the cleavage of Cu-N bonds in the presence of protons and electrons. This hypothesis is supported by various experimental studies and density functional theory calculations.

Exploring the Effects of Node Topology, Connectivity, and Metal Identity on the Binding of Nerve Agents and Their Hydrolysis Products in Metal-Organic Frameworks.

Recent studies have shown that metal-organic frameworks (MOFs) built from hexanuclear M(IV) oxide cluster nodes are effective catalysts for nerve agent hydrolysis, where the properties of the active sites on the nodes can strongly influence the reaction energetics. The connectivity and metal identity of these M6 nodes can be easily tuned, offering extensive opportunities for computational screening to predict promising new materials. Thus, we used density functional theory (DFT) to examine the effects of node topology, connectivity, and metal identity on the binding energies of multiple nerve agents and their corresponding hydrolysis products. By computing an optimization metric based on the relative binding strengths of key hydrolysis reaction species (water, agent, and bidentate-bound products), we predicted optimal M6 nodes for hydrolyzing specific nerve agent and simulant molecules, where our results are in qualitative agreement with observed experimental trends. This analysis highlighted the notion that no single metal or node topology is optimal for all possible organophosphates, suggesting that MOFs should be selected based on the agent of interest. Using the large amount of data generated from our DFT calculations, we then derived quantitative structure-activity relationship (QSAR) models to help explain the complex trends observed in the binding energies. Through linear regression, we identified the most important descriptors for describing the binding of nerve agents and their hydrolysis products to M6 nodes. These results suggested that both molecular and node properties, including both structural and chemical features, collectively contribute to the binding energetics. By performing a thorough statistical analysis, we showed that our QSAR models are capable of making quantitatively accurate binding energy predictions for nerve agents and their hydrolysis products in a wide variety of M(IV)-MOFs. The insights gained herein can be used to guide future experiments for the synthesis of MOFs with enhanced catalytic activity for organophosphate hydrolysis.

Advancement of Actinide Metal-Organic Framework Chemistry via Synthesis of Pu-UiO-66.

We report the synthesis and characterization of the first plutonium metal-organic framework (MOF). Pu-UiO-66 expands the established UiO-66 series, which includes transition metal, lanthanide, and early actinide elements in the hexanuclear nodes. The thermal stability and porosity of Pu-UiO-66 were experimentally determined, and multifaceted computational methods were used to corroborate experimental values, examine inherent defects in the framework, decipher spectroscopic signatures, and elucidate the electronic structure. The crystallization of a plutonium chain side product provides direct evidence of the competition that occurs between modulator and linker in MOF syntheses. Ultimately, the synthesis of Pu-UiO-66 demonstrates adept control of Pu(IV) coordination under hydrolysis-prone conditions, provides an opportunity to extend trends across isostructural UiO-66 frameworks, and serves as the foundation for future plutonium MOF chemistry.

Tuning Catalytic Sites on Zr6O8 Metal-Organic Framework Nodes via Ligand and Defect Chemistry Probed with tert-Butyl Alcohol Dehydration to Isobutylene.

Metal-organic frameworks (MOFs) have drawn wide attention as candidate catalysts, but some essential questions about their nature and performance have barely been addressed. (1) How do OH groups on MOF nodes act as catalytic sites? (2) What are the relationships among these groups, node defects, and MOF stability, and how do reaction conditions influence them? (3) What are the interplays between catalytic properties and transport limitations? To address these questions, we report an experimental and theoretical investigation of the catalytic dehydration of tert-butyl alcohol (TBA) used to probe the activities of OH groups of Zr6O8 nodes in the MOFs UiO-66 and MOF-808, which have different densities of vacancy sites and different pore sizes. The results show that (1) terminal node OH groups are formed as formate and/or acetate ligands present initially on the nodes react with TBA to form esters, (2) these OH groups act as catalytic sites for TBA dehydration to isobutylene, and (3) TBA also reacts to break node-linker bonds to form esters and thereby unzip the MOFs. The small pores of UiO-66 limit the access of TBA and the reaction with the formate/acetate ligands bound within the pores, whereas the larger pores of MOF-808 facilitate transport and favor reaction in the MOF interior. However, after removal of the formate and acetate ligands by reaction with methanol to form esters, interior active sites in UiO-66 become accessible for the reaction of TBA, with the activity depending on the density of defect sites with terminal OH groups. The number of vacancies on the nodes is important in determining a tradeoff between the catalytic activity of a MOF and its resistance to unzipping. Computations at the level of density functional theory show how the terminal OH groups on node vacancies act as Brønsted bases, facilitating TBA dehydration via a carbocation intermediate in an E1 mechanism; the calculations further illuminate the comparable chemistry of the unzipping.

Experimental and Quantum Mechanical Characterization of an Oxygen-Bridged Plutonium(IV) Dimer.

We report the synthesis and characterization of K4 {[PuCl2 (NO3 )3 ]2 (µ2 -O)}⋅H2 O, which contains the first known µ2 -oxo bridge between two PuIV metal centers. Adding to its uniqueness is the Pu-(µ2 -O) bond length of 2.04 Å, which is the shortest of other analogous compounds. The Pu-(µ2 -O)-Pu bridge is characterized by the mixing of s-, d-, and p-orbitals from Pu with the p-orbitals of O; the 5f-orbitals do not participate in bonding. Natural bond orbital analysis indicates that Pu and O interact through one 3c-2e σPu-O-Pu and two 3c-2e πPu-O-Pu bonding orbitals and that the electron density is highly polarized on the µ2 -O. Bond topology properties analysis indicates that the Pu-(µ2 -O) bond shares both ionic and covalent character. Quantum mechanical calculations also show that the dimer has multiconfigurational ground states, where the nonet, septet, quintet, triplet, and singlet are close in energy. This work demonstrates the interplay between experimental and computational efforts that is required to understand the chemical bonding of Pu compounds.

The Role of the Organic Solvent Polarity in Isolating Uranyl Peroxide Capsule Fragments.

Uranyl peroxide capsules are a fascinating class of polyoxometalates (POMs), discovered only in the 21st century. Understanding the reactivity between peroxide, alkali cations, and uranyl in alkaline solutions is important in nuclear science disciplines including mineralogy, nuclear energy, and legacy nuclear wastes. Here, we have developed a general procedure to isolate different fragments of the uranyl-peroxide POM capsules, using organic solvents to partially remove K+ salts from crude solids of the monomer building block UO2(O2)34- (K-U1), leading to stabilization of these reactive fragments. Higher polarity organic solvents remove more K+ salts from the crude solid, owed to higher solubility, resulting in more extensive linking of uranyl peroxide building units. By this strategy we have isolated and structurally characterized a dimer K6[(UO2)2(O2)4(OH)2]·7H2O (K-U2) and a hexamer face frequently observed in the capsules, K12[(UO2)6(O2)9(OH)6]·xH2O (K-U6). Comparing experimental and computed Raman spectra shows that these intermediates crystallize by a solid-to-solid transformation, via polymerization of the monomer building block. By small-angle X-ray scattering (SAXS), we track the conversion of the fragments to POM capsules; the reaction rate increases from K-U1 (days) < K-U2 (hours) < K-U6 (instantaneous). This study provides a general synthetic procedure to isolate metastable uranyl peroxide oligomers and control the oligomerization, which will be later applied to systems with the heavier alkalis that are even less stable.

Neptunyl Peroxide Chemistry: Synthesis and Spectroscopic Characterization of a Neptunyl Triperoxide Compound, Ca2[NpO2(O2)3]·9H2O.

Little is known about the crystal chemistry of neptunyl peroxide compounds compared to uranyl peroxide compounds, for which dozens of structures have been described. Uranyl peroxides are formed over a broad range of pH and solution conditions, but neptunyl peroxide chemistry is complicated by the ability of H2O2 to act as an oxidizing or reducing agent for Np, depending on the conditions present. The combination of Np(V) in 1 M HCl, H2O2, and CaCl2 under alkaline conditions leads to the immediate crystallization of a neptunyl triperoxide monomer, Ca2[NpO2(O2)3]·9H2O, which is the first Np(VI)-based peroxide compound to be characterized in the solid state and is isostructural to Ca2[UO2(O2)3]·9H2O. The crystal structure reveals bond distances of 1.842(7) Å that are the longest reported to date for nonbridging Np(VI)-Oyl bonds. Computational studies probe the oxidation state and bond distances of the monomer unit and differences in Raman spectra of the neptunyl and uranyl triperoxide compounds.

In Situ Formation of Unprecedented Neptunium-Oxide Wheel Clusters Stabilized in a Metal-Organic Framework.

An isostructural series of Np(V) MOFs with shp-topology were synthesized and characterized. X-ray diffraction data revealed an unusual wheel-shaped node of 18 neptunyl polyhedra stabilized in the framework. Strong distortion in local coordination of the neptunium atoms is evidenced by Np-Oyl bond lengths that lie outside the typical range for Np(V). The structure was further interrogated by Raman spectroscopy and density functional theory calculations to assign the vibrational modes.

From Transition Metals to Lanthanides to Actinides: Metal-Mediated Tuning of Electronic Properties of Isostructural Metal-Organic Frameworks.

Isostructural metal-organic frameworks (MOFs) have been prepared from a variety of metal-oxide clusters, including transition metals, lanthanides, and actinides. Experimental and calculated shifts in O-H stretching frequencies for hydroxyl groups associated with the metal-oxide nodes reveal varying electronic properties for these units, thereby offering opportunities to tune support effects for other materials deposited onto these nodes.