Negative cooperativity upon hydrogen bond-stabilized O2 adsorption in a redox-active metal-organic framework.

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

The role of cations in uranyl nanocluster association: a molecular dynamics study.

Actinyl ions can self-assemble in aqueous solution to form closed cage clusters ranging from 1.5 to 4.0 nm in diameter. The self-assembly, stability, and behavior of the nanoclusters depend on the nature of the aqueous environment, such as the pH and cations present. In this work, a classical force field for [(UO2)20(O2)30]20- (U20) peroxide nanoclusters in aqueous solution was developed from quantum-mechanical calculations. Using molecular dynamics simulations, the preferred binding sites of six cations (Li+, Na+, K+, Rb+, Cs+, and Ca2+) to the nanocluster were determined. Replica exchange molecular dynamics was used to equilibrate the structure and determine the equilibrium distribution of cations and water with respect to the nanocluster cage. In addition, the free energy barriers associated with cations entering the cluster were computed. Finally, the association of two cages was investigated by computing the free energy as a function of intercage distance. The free energy profiles reveal that the nanoclusters prefer to be associated when neutralized with divalent cations, but do not associate when neutralized with monovalent cations. This could explain the formation of tertiary structures observed experimentally.

Enhanced Fe-Centered Redox Flexibility in Fe-Ti Heterobimetallic Complexes.

Previously, we reported the synthesis of Ti[N( o-(NCH2P( iPr)2)C6H4)3] and the Fe-Ti complex, FeTi[N( o-(NCH2P( iPr)2)C6H4)3], abbreviated as TiL (1), and FeTiL (2), respectively. Herein, we describe the synthesis and characterization of the complete redox families of the monometallic Ti and Fe-Ti compounds. Cyclic voltammetry studies on FeTiL reveal both reduction and oxidation processes at -2.16 and -1.36 V (versus Fc/Fc+), respectively. Two isostructural redox members, [FeTiL]+ and [FeTiL]- (2ox and 2red, respectively) were synthesized and characterized, along with BrFeTiL (2-Br) and the monometallic [TiL]+ complex (1ox). The solid-state structures of the [FeTiL]+/0/- series feature short metal-metal bonds, ranging from 1.94-2.38 Å, which are all shorter than the sum of the Ti and Fe single-bond metallic radii (cf. 2.49 Å). To elucidate the bonding and electronic structures, the complexes were characterized with a host of spectroscopic methods, including NMR, EPR, and 57Fe Mössbauer, as well as Ti and Fe K-edge X-ray absorption spectroscopy (XAS). These studies, along with hybrid density functional theory (DFT) and time-dependent DFT calculations, suggest that the redox processes in the isostructural [FeTiL]+,0,- series are primarily Fe-based and that the polarized Fe-Ti π-bonds play a role in delocalizing some of the additional electron density from Fe to Ti (net 13%).

Density matrix renormalization group pair-density functional theory (DMRG-PDFT): singlet-triplet gaps in polyacenes and polyacetylenes.

The density matrix renormalization group (DMRG) is a powerful method to treat static correlation. Here we present an inexpensive way to calculate correlation energy starting from a DMRG wave function using pair-density functional theory (PDFT). We applied this new approach, called DMRG-PDFT, to study singlet-triplet gaps in polyacenes and polyacetylenes that require active spaces larger than the feasibility limit of the conventional complete active-space self-consistent field (CASSCF) method. The results match reasonably well with the most reliable literature values and have only a moderate dependence on the compression of the initial DMRG wave function. Furthermore, DMRG-PDFT is significantly less expensive than other commonly applied ways of adding additional correlation to DMRG, such as DMRG followed by multireference perturbation theory or multireference configuration interaction.

Rhodium catalyzed hydroformylation of olefins.

DFT and CCSD(T) methods were used to examine 61 different rhodium catalysts for the hydroformylation of ethylene. The carbon monoxide (CO) stretching frequency was a key electronic parameter to understand the π-accepting nature of the ligand. Normally, π-accepting ligands lead to increased CO stretching frequencies and a reduction in CO dissociation energy. There was no relationship between CO dissociation energy and CO stretching frequency. However, a clear relationship exists between the ethylene insertion barrier (from the rhodium dicarbonyl hydride resting state) and the CO stretching frequency as stronger π-accepting ligands systematically led to a reduction in the barrier. Due to the multistep nature of the rate-limiting step, the overall barrier can be divided into the CO/ethylene equilibrium and an intrinsic ethylene insertion barrier and both are systematically reduced as the π-accepting nature of the ligand is increased. A comparison of the carbonylation transition state (TS) to the ethylene insertion TS allowed us to understand reversibility of olefin insertion. While the ethylene insertion TS systematically decreases with increasing CO stretching frequency, the carbonylation TS is relatively flat. The lines cross at 2156 cm-1 implying a change in the rate-limiting step in this region given a standard set of process conditions. © 2018 Wiley Periodicals, Inc.

Valence ππ* Excitations in Benzene Studied by Multiconfiguration Pair-Density Functional Theory.

We explore the valence singlet and triplet ππ* excitations of benzene with complete active pace self-consistent field (CASSCF) theory, complete active space perturbation theory (CASPT2), and multiconfiguration pair-density functional theory (MC-PDFT) for four different choices of active space. We propose a new way to quantify the covalent and ionic character of the electronic states in terms of the components of the total electronic energy. We also explore the effect of scaling the exchange and correlation components of the on-top density functional used in MC-PDFT; we observe that increasing the exchange contribution improves the MC-PDFT excitation energies for benzene.

Structure and Dynamics of Zr6O8 Metal-Organic Framework Node Surfaces Probed with Ethanol Dehydration as a Catalytic Test Reaction.

Some metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters such as Zr6O8. Vacancies on the node surfaces, accidental or by design, act as catalytic sites. Here, we report elucidation of the chemistry of Zr6O8 nodes in the MOFs UiO-66 and UiO-67 having used infrared and nuclear magnetic resonance spectroscopies to determine the ligands on the node surfaces originating from the solvents and modifiers used in the syntheses and having elucidated the catalytic properties of the nodes for ethanol dehydration, which takes place selectively to make diethyl ether but not ethylene at 473-523 K. Density functional theory calculations show that the key to the selective catalysis is the breaking of node-linker bonds (or the accidental adjacency of open/defect sites) that allows catalytically fruitful bonding of the reactant ethanol to neighboring sites on the nodes, facilitating the bimolecular ether formation through an SN2 mechanism.

Can Density Matrix Embedding Theory with the Complete Activate Space Self-Consistent Field Solver Describe Single and Double Bond Breaking in Molecular Systems?

Density matrix embedding theory (DMET) [ Phys. Rev. Lett. 2012, 109, 186404] has been demonstrated as an efficient wave-function-based embedding method to treat extended systems. Despite its success in many quantum lattice models, the extension of DMET to real chemical systems has been tested only on selected cases. Herein, we introduce the use of the complete active space self-consistent field (CASSCF) method as a correlated impurity solver for DMET, leading to a method called CAS-DMET. We test its performance in describing the dissociation of H-H single bonds in a H10 ring model system and an N═N double bond in azomethane (CH3-N═N-CH3) and pentyldiazene (CH3(CH2)4-N═NH). We find that the performance of CAS-DMET is comparable to CASSCF with different active space choices when single-embedding DMET corresponding to only one embedding problem for the system is used. When multiple embedding problems are used for the system, the CAS-DMET is in good agreement with CASSCF for the geometries around the equilibrium, but not in equal agreement at bond dissociation.

Computational Design of Functionalized Metal-Organic Framework Nodes for Catalysis.

Recent progress in the synthesis and characterization of metal-organic frameworks (MOFs) has opened the door to an increasing number of possible catalytic applications. The great versatility of MOFs creates a large chemical space, whose thorough experimental examination becomes practically impossible. Therefore, computational modeling is a key tool to support, rationalize, and guide experimental efforts. In this outlook we survey the main methodologies employed to model MOFs for catalysis, and we review selected recent studies on the functionalization of their nodes. We pay special attention to catalytic applications involving natural gas conversion.

Bridging Zirconia Nodes within a Metal-Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires.

Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged as a versatile approach to functionalize MOF surfaces with a wide variety of catalytic metal-oxo species. Understanding the structure of newly deposited species and how they are tethered within the MOF is critical to understanding how these components couple to govern the active material properties. By combining local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis, and difference envelope density analysis, with electron microscopy imaging and computational modeling, we resolve the precise atomic structure of metal-oxo species deposited in the MOF NU-1000 through ALD. These analyses demonstrate that deposition of NiOxHy clusters occurs selectively within the smallest pores of NU-1000, between the zirconia nodes, serving to connect these nodes along the c-direction to yield heterobimetallic metal-oxo nanowires. This bridging motif perturbs the NU-1000 framework structure, drawing the zirconia nodes closer together, and also underlies the sintering resistance of these clusters during the hydrogenation of light olefins.

Molecular Rhodium Complexes Supported on the Metal-Oxide-Like Nodes of Metal Organic Frameworks and on Zeolite HY: Catalysts for Ethylene Hydrogenation and Dimerization.

Metal-organic frameworks (MOFs) with nodes consisting of zirconium oxide clusters (Zr6) offer new opportunities as supports for catalysts with well-defined, essentially molecular, structures. We used the precursor Rh(C2H4)2(acac) (acac is acetylacetonate) to anchor Rh(I) complexes to the nodes of the MOF UiO-67 and, for comparison, to the zeolite dealuminated HY (DAY). These were characterized experimentally by measurement of catalytic activities and selectivities for ethylene hydrogenation and dimerization in a once-through flow reactor at 298 K and 1 bar. The catalyst performance data are complemented with structural information determined by infrared and extended X-ray absorption fine structure spectroscopies and by calculations at the level of density functional theory, the latter carried out also to extend the investigation to a related MOF, NU-1000. The agreement between the experimental and calculated structural metrics is good, and the calculations have led to predictions of reaction mechanisms and associated energetics. The data demonstrate a correlation between the catalytic activity and selectivity and the electron-donor tendency of the supported rhodium (as measured by the frequencies of CO ligands bonded as probes to the Rh(I) centers), which is itself a measure of the electron-donor tendency of the support.

Metal-Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane at Low Temperature.

Zr-based metal-organic frameworks (MOFs) have been shown to be excellent catalyst supports in heterogeneous catalysis due to their exceptional stability. Additionally, their crystalline nature affords the opportunity for molecular level characterization of both the support and the catalytically active site, facilitating mechanistic investigations of the catalytic process. We describe herein the installation of Co(II) ions to the Zr6 nodes of the mesoporous MOF, NU-1000, via two distinct routes, namely, solvothermal deposition in a MOF (SIM) and atomic layer deposition in a MOF (AIM), denoted as Co-SIM+NU-1000 and Co-AIM+NU-1000, respectively. The location of the deposited Co species in the two materials is determined via difference envelope density (DED) analysis. Upon activation in a flow of O2 at 230 °C, both materials catalyze the oxidative dehydrogenation (ODH) of propane to propene under mild conditions. Catalytic activity as well as propene selectivity of these two catalysts, however, is different under the same experimental conditions due to differences in the Co species generated in these two materials upon activation as observed by in situ X-ray absorption spectroscopy. A potential reaction mechanism for the propane ODH process catalyzed by Co-SIM+NU-1000 is proposed, yielding a low activation energy barrier which is in accord with the observed catalytic activity at low temperature.

Uranyl Peroxide Cage Cluster Solubility in Water and the Role of the Electrical Double Layer.

Uranium concentrations as high as 2.94 × 105 parts per million (1.82 mol of U/1 kg of H2O) occur in water containing nanoscale uranyl cage clusters. The anionic cage clusters, with diameters of 1.5-2.5 nm, are charge-balanced by encapsulated cations, as well as cations within their electrical double layer in solution. The concentration of uranium in these systems is impacted by the countercations (K, Li, Na), and molecular dynamics simulations have predicted their distributions in selected cases. Formation of uranyl cages prevents hydrolysis reactions that would result in formation of insoluble uranyl solids under alkaline conditions, and these spherical clusters reach concentrations that require close packing in solution.

Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes.

Combination of uranium, peroxide, and mono- (Na, K) or divalent (Mg, Ca, Sr) cations under alkaline aqueous conditions results in the rapid formation of anionic uranyl triperoxide monomers (UTs), (UO2(O2)3)4-, exhibiting unique Raman signatures. Electronic structure calculations were decisive for the interpretation of the spectra and assignment of unexpected signals associated with vibrations of the uranyl and peroxide ions. Assignments were verified by 18O isotopic labeling of the uranyl ions supporting the computational-based interpretation of the experimentally observed peaks and the assignment of a novel asymmetric vibration of the peroxide ligands, v2(O22-).

Structural and Spectroscopic Characterization of Reaction Intermediates Involved in a Dinuclear Co-Hbpp Water Oxidation Catalyst.

An end-on superoxido complex with the formula {[CoIII(OH2)(trpy)][CoIII(OO•)(trpy)](µ-bpp)}4+ (34+) (bpp- = bis(2-pyridyl)-3,5-pyrazolate; trpy = 2,2';6':2″-terpyridine) has been characterized by resonance Raman, electron paramagnetic resonance, and X-ray absorption spectroscopies. These results together with online mass spectrometry experiments using 17O and 18O isotopically labeled compounds prove that this compound is a key intermediate of the water oxidation reaction catalyzed by the peroxido-bridged complex {[CoIII(trpy)]2(µ-bpp)(µ-OO)}3+ (13+). DFT calculations agree with and complement the experimental data, offering a complete description of the transition states and intermediates involved in the catalytic cycle.

Tuning the Surface Chemistry of Metal Organic Framework Nodes: Proton Topology of the Metal-Oxide-Like Zr6 Nodes of UiO-66 and NU-1000.

Some metal organic frameworks (MOFs) incorporate nodes that are nanoscale metal oxides, and the hydroxy-containing functional groups on them provide opportunities for introducing catalytic sites with precisely defined structures. Investigations have been done to understand the structures of these groups on nodes and node vacancies, because, in prospect, atomic-scale modulation of the composition, areal density, and/or siting of the groups would open up possibilities for exquisite tuning of the siting and performance of subsequently anchored catalytic units (e.g., single metal ions, pairs of metal ions, or well-defined metal-ion-containing clusters). We have combined infrared (IR) spectroscopy and density functional theory (DFT) to demonstrate tuning of these sites, namely, hydrogen-bonded OH/OH2 groups on the Zr6 nodes of the MOFs UiO-66 and NU-1000 via the intermediacy of node methoxy (or ethoxy) groups formed from methanol (or ethanol). Methoxy (or ethoxy) groups on node vacancy sites are converted to a structure incorporating one vacant Zr site and one terminal OH group per face by reaction with water. Our results highlight how the combination of DFT and IR spectroscopy facilitates the determination of the identity and chemistry of the functional groups on MOF node vacancies and defect sites.

Unprecedented selectivity in molecular recognition of carbohydrates by a metal-organic framework.

Metal-organic framework (MOF) material NU-1000 adsorbs dimers cellobiose and lactose from aqueous solution, in amounts exceeding 1250 mg gNU-1000(-1) while completely excluding the adsorption of the monomer glucose, even in a competitive mode with cellobiose. The MOF also discriminates between dimers consisting of α and ß linkages, showing no adsorption of maltose. Electronic structure calculations demonstrate that key to this selective molecular recognition is the number of favorable CH-π interactions made by the sugar with pyrene units of the MOF.

Sintering-Resistant Single-Site Nickel Catalyst Supported by Metal-Organic Framework.

Developing supported single-site catalysts is an important goal in heterogeneous catalysis since the well-defined active sites afford opportunities for detailed mechanistic studies, thereby facilitating the design of improved catalysts. We present herein a method for installing Ni ions uniformly and precisely on the node of a Zr-based metal-organic framework (MOF), NU-1000, in high density and large quantity (denoted as Ni-AIM) using atomic layer deposition (ALD) in a MOF (AIM). Ni-AIM is demonstrated to be an efficient gas-phase hydrogenation catalyst upon activation. The structure of the active sites in Ni-AIM is proposed, revealing its single-site nature. More importantly, due to the organic linker used to construct the MOF support, the Ni ions stay isolated throughout the hydrogenation catalysis, in accord with its long-term stability. A quantum chemical characterization of the catalyst and the catalytic process complements the experimental results. With validation of computational modeling protocols, we further targeted ethylene oligomerization catalysis by Ni-AIM guided by theoretical prediction. Given the generality of the AIM methodology, this emerging class of materials should prove ripe for the discovery of new catalysts for the transformation of volatile substrates.

Heterobimetallic Complexes That Bond Vanadium to Iron, Cobalt, and Nickel.

Zero-valent iron, cobalt, and nickel were installed into the metalloligand V[N(o-(NCH2P((i)Pr)2)C6H4)3] (1, VL), generating the heterobimetallic trio FeVL (2), CoVL (3), and NiVL (4), respectively. In addition, the one-electron-oxidized analogues [FeVL]X ([2(ox)]X, where X(-) = BPh4 or PF6) and [CoVL]BPh4 ([3(ox)]BPh4) were prepared. The complexes were characterized by a host of physical methods, including cyclic voltammetry, X-ray crystallography, magnetic susceptibility, electronic absorption, NMR, electron paramagnetic resonance (EPR), and Mössbauer spectroscopies. The CoV and FeV heterobimetallic compounds have short M-V bond lengths that are consistent with M-M multiple bonding. As revealed by theoretical calculations, the M-V bond is triple in 2, 2(ox), and 3(ox), double in 3, and dative (Ni → V) in 4. The (d-d)(10) species, 2 and 3(ox), are diamagnetic and exhibit large diamagnetic anisotropies of -4700 × 10(-36) m(3)/molecule. Complexes 2 and 3(ox) are also characterized by intense visible bands at 760 and 610 nm (ε > 1000 M(-1) cm(-1)), respectively, which correspond to an intermetal (M → V) charge-transfer transition. Magnetic susceptibility measurements and EPR characterization establish S = (1)/2 ground states for (d-d)(9) 2(ox) and (d-d)(11) 3, while (d-d)(12) 4 is S = 1 based on Evans' method.

Bimetallic cobalt-dinitrogen complexes: impact of the supporting metal on N2 activation.

Expanding a family of cobalt bimetallic complexes, we report the synthesis of the Ti(III) metalloligand, Ti[N(o-(NCH2P((i)Pr)2)C6H4)3] (abbreviated as TiL), and three heterobimetallics that pair cobalt with an early transition metal ion: CoTiL (1), K(crypt-222)[(N2)CoVL] (2), and K(crypt-222)[(N2)CoCrL] (3). The latter two complexes, along with previously reported K(crypt-222)[(N2)CoAlL] and K(crypt-222)[(N2)Co2L], constitute an isostructural series of cobalt bimetallics that bind dinitrogen in an end-on fashion, i.e. [(N2)CoML](-). The characterization of 1-3 includes cyclic voltammetry, X-ray crystallography, and infrared spectroscopy. The [CoTiL](0/-) reduction potential is extremely negative at -3.20 V versus Fc(+)/Fc. In the CoML series where M is a transition metal, the reduction potentials shift anodically as M is varied across the first-row period. Among the [(N2)CoML](-) compounds, the dinitrogen ligand is weakly activated, as evidenced by N-N bond lengths between 1.110(8) and 1.135(4) Å and by N-N stretching frequencies between 1971 and 1995 cm(-1). Though changes in νN2 are subtle, the extent of N2 activation decreases across the first-row period. A correlation is found between the [CoML](0/-) reduction potentials and N2 activation, where the more cathodic potentials correspond to lower N-N frequencies. Theoretical calculations of the [(N2)CoML](-) complexes reveal important variations in the electronic structure and Co-M interactions, which depend on the exact nature of the supporting metal ion, M.