Hydrogen adsorption in the metal-organic frameworks Fe2(dobdc) and Fe2(O2)(dobdc)

The hydrogen storage properties of Fe(2)(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) and an oxidized analog, Fe(2)(O(2))(dobdc), have been examined using several complementary techniques, including low-pressure gas adsorption, neutron powder diffraction, and inelastic neutron scattering. These two metal-organic frameworks, which possess one-dimensional hexagonal channels decorated with unsaturated iron coordination sites, exhibit high initial isosteric heats of adsorption of -9.7(1) and -10.0(1) kJ mol(-1), respectively. Neutron powder diffraction has allowed the identification of three D(2) binding sites within the two frameworks, with the closest contacts corresponding to Fe-D(2) separations of 2.47(3) and 2.53(5) ?, respectively. Inelastic neutron scattering spectra, obtained from p-H(2) (para-H(2)) and D(2)-p-H(2) mixtures adsorbed in Fe(2)(dobdc), reveal weak interactions between two neighboring adsorption sites, a finding that is in opposition to a previous report of possible 'pairing' between neighboring H(2) molecules.     

Selective binding of O2 over N2 in a redox-active metal-organic framework with open iron(II) coordination sites

The air-free reaction between FeCl(2) and H(4)dobdc (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate) in a mixture of N,N-dimethylformamide (DMF) and methanol affords Fe(2)(dobdc)·4DMF, a metal-organic framework adopting the MOF-74 (or CPO-27) structure type. The desolvated form of this material displays a Brunauer-Emmett-Teller (BET) surface area of 1360 m(2)/g and features a hexagonal array of one-dimensional channels lined with coordinatively unsaturated Fe(II) centers. Gas adsorption isotherms at 298 K indicate that Fe(2)(dobdc) binds O(2) preferentially over N(2), with an irreversible capacity of 9.3 wt %, corresponding to the adsorption of one O(2) molecule per two iron centers. Remarkably, at 211 K, O(2) uptake is fully reversible and the capacity increases to 18.2 wt %, corresponding to the adsorption of one O(2) molecule per iron center. Mo?ssbauer and infrared spectra are consistent with partial charge transfer from iron(II) to O(2) at low temperature and complete charge transfer to form iron(III) and O(2)(2-) at room temperature. The results of Rietveld analyses of powder neutron diffraction data (4 K) confirm this interpretation, revealing O(2) bound to iron in a symmetric side-on mode with d(O-O) = 1.25(1) ? at low temperature and in a slipped side-on mode with d(O-O) = 1.6(1) ? when oxidized at room temperature. Application of ideal adsorbed solution theory in simulating breakthrough curves shows Fe(2)(dobdc) to be a promising material for the separation of O(2) from air at temperatures well above those currently employed in industrial settings.     

Hydrogen storage properties and neutron scattering studies of Mg2(dobdc)--a metal-organic framework with open Mg2+ adsorption sites

The hydrogen storage properties of Mg(2)(dobdc) (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate), a metal-organic framework possessing hexagonal one-dimensional channels decorated with unsaturated Mg(2+) coordination sites, have been examined through low- and high-pressure adsorption experiments, infrared spectroscopy, and neutron scattering studies.     

Role of exposed metal sites in hydrogen storage in MOFs

The role of exposed metal sites in increasing the H2 storage performances in metal-organic frameworks (MOFs) has been investigated by means of IR spectrometry. Three MOFs have been considered: MOF-5, with unexposed metal sites, and HKUST-1 and CPO-27-Ni, with exposed Cu(2+) and Ni(2+), respectively. The onset temperature of spectroscopic features associated with adsorbed H2 correlates with the adsorption enthalpy obtained by the VTIR method and with the shift experienced by the H-H stretching frequency. This relationship can be ascribed to the different nature and accessibility of the metal sites. On the basis of a pure energetic evaluation, it was observed that the best performance was shown by CPO-27-Ni that exhibits also an initial adsorption enthalpy of -13.5 kJ mol(-1), the highest yet observed for a MOF. Unfortunately, upon comparison of the hydrogen amounts stored at high pressure, the hydrogen capacities in these conditions are mostly dependent on the surface area and total pore volume of the material. This means that if control of MOF surface area can benefit the total stored amounts, only the presence of a great number of strong adsorption sites can make the (P, T) storage conditions more economically favorable. These observations lead to the prediction that efficient H2 storage by physisorption can be obtained by increasing the surface density of strong adsorption sites.     

CO(2) Dynamics in a Metal-Organic Framework with Open Metal Sites

Metal-organic frameworks (MOFs) with open metal sites are promising candidates for CO(2) capture from dry flue gas. We applied in situ(13)C NMR spectroscopy to investigate CO(2) adsorbed in Mg(2)(dobdc) (H(4)dobdc = 2,5-dihydroxyterephthalic acid; Mg-MOF-74, CPO-27-Mg), a key MOF in which exposed Mg(2+) cation sites give rise to exceptional CO(2) capture properties. Analysis of the resulting spectra reveals details of the binding and CO(2) rotational motion within the material. The dynamics of the motional processes are evaluated via analysis of the NMR line shapes and relaxation times observed between 12 and 400 K. These results form stringent and quantifiable metrics for computer simulations that seek to screen and improve the design of new MOFs for CO(2) capture.     

Metal-organic frameworks as adsorbents for hydrogen purification and precombustion carbon dioxide capture

Selected metal-organic frameworks exhibiting representative properties--high surface area, structural flexibility, or the presence of open metal cation sites--were tested for utility in the separation of CO(2) from H(2) via pressure swing adsorption. Single-component CO(2) and H(2) adsorption isotherms were measured at 313 K and pressures up to 40 bar for Zn(4)O(BTB)(2) (MOF-177, BTB(3-) = 1,3,5-benzenetribenzoate), Be(12)(OH)(12)(BTB)(4) (Be-BTB), Co(BDP) (BDP(2-) = 1,4-benzenedipyrazolate), H(3)[(Cu(4)Cl)(3)(BTTri)(8)] (Cu-BTTri, BTTri(3-) = 1,3,5-benzenetristriazolate), and Mg(2)(dobdc) (dobdc(4-) = 1,4-dioxido-2,5-benzenedicarboxylate). Ideal adsorbed solution theory was used to estimate realistic isotherms for the 80:20 and 60:40 H(2)/CO(2) gas mixtures relevant to H(2) purification and precombustion CO(2) capture, respectively. In the former case, the results afford CO(2)/H(2) selectivities between 2 and 860 and mixed-gas working capacities, assuming a 1 bar purge pressure, as high as 8.6 mol/kg and 7.4 mol/L. In particular, metal-organic frameworks with a high concentration of exposed metal cation sites, Mg(2)(dobdc) and Cu-BTTri, offer significant improvements over commonly used adsorbents, indicating the promise of such materials for applications in CO(2)/H(2) separations.     

Controlled Synthesis of Large Single Crystals of Metal-Organic Framework CPO-27-Ni Prepared by a Modulation Approach: In situ Single-Crystal X-ray Diffraction Studies

The size of single crystals of the metal-organic framework CPO-27-Ni was incrementally increased through a series of modulated syntheses. A novel linker modulated synthesis using 2,5-dihydroxyterephthalic acid and the isomeric ligand 4,6-dihydroxyisophthalic acid yielded large single crystals of CPO-27-Ni (∼70 μm). All materials were shown to have high crystallinity and phase purity through powder X-ray diffraction, electron microscopy methods, thermogravimetry, and compositional analysis. For the first time single-crystal structure analyses were carried out on CPO-27-Ni. High BET surface areas and nitric oxide (NO) release efficiencies were recorded for all materials. Large single crystals of CPO-27-Ni showed a prolonged NO release and proved suitable for in situ single-crystal diffraction experiments to follow the NO adsorption. An efficient activation protocol was developed, leading to a dehydrated structure after just 4 h, which subsequently was NO-loaded, leading to a first NO loaded single-crystal structural model of CPO-27-Ni.     

Effect of Larger Pore Size on the Sorption Properties of Isoreticular Metal–Organic Frameworks with High Number of Open Metal Sites

Four isostructural CPO-54-M metal-organic frameworks based on the larger organic linker 1,5-dihydroxynaphthalene-2,6-dicarboxylic acid and divalent cations (M=Mn, Mg, Ni, Co) are shown to be isoreticular to the CPO-27 (MOF-74) materials. Desolvated CPO-54-Mn contains a very high concentration of open metal sites, which has a pronounced effect on the gas adsorption of N₂, H₂, CO₂ and CO. Initial isosteric heats of adsorption are significantly higher than for MOFs without open metal sites and are slightly higher than for CPO-27. The plateau of high heat of adsorption decreases earlier in CPO-54-Mn as a function of loading per mole than in CPO-27-Mn. Cluster and periodic density functional theory based calculations of the adsorbate structures and energetics show that the larger adsorption energy at low loadings, when only open metal sites are occupied, is mainly due to larger contribution of dispersive interactions for the materials with the larger, more electron rich bridging ligand.     

Ligand Steric and Fluoroalkyl Substituent Effects on Enchainment Cooperativity and Stability in Bimetallic Nickel(II) Polymerization Catalysts

The synthesis and characterization of two neutrally charged bimetallic Ni(II) ethylene polymerization catalysts, {2,7-di-[2,6-(3,5-di-methylphenylimino)methyl]1,8-naphthalenediolato}-bis-Ni(II) (methyl)(trimethylphosphine) [(CH(3) )FI(2) -Ni(2) ] and {2,7-di-[2,6-(3,5-di-trifluoromethyl-phenylimino)methyl]-1,8-naphthalenediolato}-bis-Ni(II) (methyl)(trimethyl-phosphine) [(CF(3) )FI(2) -Ni(2) )], are reported. The diffraction-derived molecular structure of (CF(3) )FI(2) -Ni(2) reveals a Ni???Ni distance of 5.8024(5)??. In the presence of ethylene and Ni(COD)(2) or B(C(6) F(5) )(3) co-catalysts, these complexes along with their monometallic analogues [2-tert-butyl-6-((2,6-(3,5-dimethylphenyl)phenylimino)methyl)-phenolate]-Ni(II) -methyl(trimethylphosphine) [(CH(3) )FI-Ni] and [2-tert-butyl-6-((2,6-(3,5-ditrifluoromethyl-phenyl)phenylimino)methyl)phenolato]-Ni(II) -methyl-(trimethylphosphine) [(CF(3) )FI-Ni], produce polyethylenes ranging from highly branched M(w) =1400 oligomers (91?methyl branches per 1000?C) to low branch density M(w) =92?000 polyethylenes (7?methyl branches per 1000?C). In the bimetallic catalysts, Ni???Ni cooperative effects are evidenced by increased product polyethylene branching in ethylene homopolymerizations (～3× for (CF(3) )FI(2) -Ni(2) vs. monometallic (CF(3) )FI-Ni), as well as by enhanced norbornene co-monomer incorporation selectivity, with bimetallic (CH(3) )FI(2) -Ni(2) and (CF(3) )FI(2) -Ni(2) enchaining approximately three- and six-times more norbornene, respectively, than monometallic (CH(3) )FI-Ni and (CF(3) )FI-Ni. Additionally, (CH(3) )FI(2) -Ni(2) and (CF(3) )FI(2) -Ni(2) exhibit significantly enhanced thermal stability versus the less sterically encumbered dinickel catalyst {2,7-di-[(2,6-diisopropylphenyl)imino]-1,8-naphthalenediolato}-bis-Ni(II) (methyl)(trimethylphosphine). The pathway for bimetallic catalyst thermal deactivation is shown to involve an unexpected polymerization-active intermediate, {2,7-di-[2,6-(3,5-di-trifluoromethyl-phenylimino)methyl]-1-hydroxy,8-naphthalenediolato-Ni(II) (methyl)-(trimethylphosphine).     

Adsorption properties and structure of CO2 adsorbed on open coordination sites of metal-organic framework Ni2(dhtp) from gas adsorption, IR spectroscopy and X-ray diffraction

The microporous metal-organic framework Ni(2)(dhtp) (H(4)dhtp=2,5-dihydroxyterephthalic acid) shows distinct end-on CO(2) coordination to coordinatively unsaturated nickel sites giving rise to high CO(2) adsorption capacity at sub-atmospheric pressures and ambient temperatures.     

Three-dimensional metal-organic framework with highly polar pore surface: H2 and CO2 storage characteristics

A three-dimensional (3D) pillared-layer metal-organic framework, [Cd(bipy)(0.5)(Himdc)](DMF)](n) (1), (bipy =4,4'-bipyridine and Himdc = 4,5-imidazoledicarboxylate) has been synthesized and structurally characterized. The highly rigid and stable framework contains a 3D channel structure with highly polar pore surfaces decorated with pendant oxygen atoms of the Himdc linkers. The desolvated framework [Cd(bipy)(0.5)(Himdc)](n) (1') is found to exhibit permanent porosity with high H(2) and CO(2) storage capacities. Two H(2) molecules occluded per unit formula of 1' and the corresponding heat of H(2) adsorption (ΔH(H2)) is about ～9.0 kJ/mol. The high value of ΔH(H2) stems from the preferential electrostatic interaction of H(2) with the pendent oxygen atoms of Himdc and aromatic bipy linkers as determined from first-principles density functional theory (DFT) based calculations. Similarly, DFT studies indicate CO(2) to preferentially interact electrostatically (C(δ+)···O(δ-)) with the uncoordinated pendent oxygen of Himdc. It also interacts with bipy through C-H···O bonding, thus rationalizing the high heat (ΔH(CO2) ～ 35.4 kJ/mol) of CO(2) uptake. Our work unveiled that better H(2) or CO(2) storage materials can be developed through the immobilization of reactive hetero atoms (O, N) at the pore surfaces in a metal-organic framework.     

Enhanced CO2 binding affinity of a high-uptake rht-type metal-organic framework decorated with acylamide groups

An rht-type metal-organic framework (MOF) prepared from M(2)(carboxylate)(4) (M = Cu, Co) paddlewheel clusters and a flexible C(3)-symmetric hexacarboxylate ligand with acylamide groups exhibits larger CO(2) uptake, an enhanced heat of adsorption, and higher selectivity toward CO(2)/N(2) in comparison with what was previously observed for an analogous MOF with alkyne groups.     

Novel (3,4,6)-connected metal-organic framework with high stability and gas-uptake capability

A microporous and noninterpenetrated metal-organic framework [Cu(3)(L)(2)(DABCO)(H(2)O)]·15H(2)O·9DMF (1) has been synthesized using two different ligands, [1,1':3',1″-terphenyl]-4,4″,5'-tricarboxylic acid (H(3)L) and 1,4-diazabicyclo[2.2.2]octane (DABCO). As revealed by variable-temperature powder X-ray diffraction (VT-PXRD) measurements, N,N'-ditopic DABCO plays an important role for stabilization of the Cu-L framework. The three-dimensional framework of 1 exhibits high stability and excellent adsorption capacity for H(2) (54.3 mg g(-1) at 77 K and 20 bar), CO(2) (871 mg g(-1) at 298 K and 20 bar), CH(4) (116.7 mg g(-1), 99 cm(3) (STP) cm(-3) at 298 K and 20 bar), and n-pentane (686 mg g(-1) at 298 K and 1 bar). Interestingly, the excellent selectivity toward CO(2) over N(2) at ambient temperature (273 and 298 K) and 1 bar makes complex 1 possess practical application in gas separation and purification.     

Highly selective carbon dioxide uptake by [Cu(bpy-n)2(SiF6)] (bpy-1 = 4,4'-bipyridine; bpy-2 = 1,2-bis(4-pyridyl)ethene)

A previously known class of porous coordination polymer (PCP) of formula [Cu(bpy-n)(2)(SiF(6))] (bpy-1 = 4,4'-bipyridine; bpy-2 = 1,2-bis(4-pyridyl)ethene) has been studied to assess its selectivity toward CO(2), CH(4), N(2), and H(2)O. Gas sorption measurements reveal that [Cu(bpy-1)(2)(SiF(6))] exhibits the highest uptake for CO(2) yet seen at 298 K and 1 atm by a PCP that does not contain open metal sites. Significantly, [Cu(bpy-1)(2)(SiF(6))] does not exhibit particularly high uptake under the same conditions for CH(4), N(2), and, H(2)O, presumably because of its lack of open metal sites. Consequently, at 298 K and 1 atm [Cu(bpy-1)(2)(SiF(6))] exhibits a relative uptake of CO(2) over CH(4) of ca. 10.5:1, the highest value experimentally observed in a compound without open metal sites. [Cu(bpy-2)(2)(SiF(6))] exhibits larger pores and surface area than [Cu(bpy-1)(2)(SiF(6))] but retains a high CO(2)/CH(4) relative uptake of ca. 8:1.     

Mn(II)-based porous metal-organic framework showing metamagnetic properties and high hydrogen adsorption at low pressure

A Mn(II)-based homometallic porous metal-organic framework, Mn(5)(btac)(4)(μ(3)-OH)(2)(EtOH)(2)·DMF·3EtOH·3H(2)O (1, btac = benzotriazole-5-carboxylate), has been solvothermally synthesized and structurally characterized by elemental analysis, thermogravimetric analysis, and X-ray crystallographic study. 1 is a 3D neutral framework featuring 1D porous channels constructed by {Mn-OH-Mn}(n) chains and btac linkers. Magnetic studies show that 1 is a 3D metamagnet containing 1D {Mn-OH-Mn}(n) ferrimagnetic chains. High-pressure H(2) adsorption measurement at 77 K reveals that activated 1 can absorb 0.99 wt % H(2) at 0.5 atm and reaches a maximum of 1.03 wt % at 5.5 atm. The steep H(2) absorption at lower pressure (98.2% of the storage capacity at 0.5 atm) is higher than the corresponding values of some MOFs (MIL-100 (16.1%), MOF-177 (57.1%), and MOF-5 (22.2%)). Furthermore, activated 1 can adsorb CO(2) at room temperature and 275 K. The adsorption enthalpy is 22.0 kJ mol(-1), which reveals the high binding ability for CO(2). Detailed gas sorption implies that the exposed Mn(II) coordination sites in the activated 1 play an important role to improve its adsorption capacities.     

A contrivance for a dynamic porous framework: cooperative guest adsorption based on square grids connected by amide-amide hydrogen bonds

Flexible porous coordination polymers containing amide groups as a function origin have been synthesized and categorized as "Coordination Polymer with Amide Groups". Bispyridyl ligands with a spacer of amide group afford two-dimensional (2-D) motifs with a deformed square grid, resulting in three-dimensional (3-D) frameworks of [Co(NO(3))(2)(3-pna)(2)](n)(1), [Co(Br)(2)(3-pna)(2)](n)(2), and [[Co(NCS)(2)(4-peia)(2)].4Me(2)CO](n)(3 subset 4Me(2)CO) (3-pna = N-3-pyridylnicotinamide, 4-peia = N-(2-pyridin-4-yl-ethyl)-isonicotinamide), where the 2-D motifs are bound by complementary hydrogen bond between the amide groups. In the case of the 3 subset 4Me(2)CO, the amide groups form a contrivance for a dynamic porous framework because of their relevant position and orientation in the mutual nearest neighboring motifs. Consequently, 3 subset 4Me(2)CO shows amorphous (nonporous)-to-crystal (porous) structural rearrangement in the Me(2)CO adsorption and desorption process, where the framework of the 2-D motif is maintained. The adsorption isotherm has threshold pressure (P(th)), a sort of gate pressure. The heat of Me(2)CO adsorption (DeltaH(ad) = -25 kJ/mol) is obtained from the temperature dependence of threshold pressure (P(th)), which is close to acetone vaporization enthalpy (DeltaH(vap) = 30.99 kJ/mol).     

Atomic alignment effect in the dissociative energy transfer reaction of metal carbonyls (Fe(CO)5, Ni(CO)4) with oriented Ar (3P2, M(J) = 2)

The atomic alignment effect has been studied for the dissociative energy transfer reaction of metal carbonyls (Fe(CO)(5), Ni(CO)(4)) with the oriented Ar ((3)P(2), M(J) = 2). The emission intensity from the excited metal products (Fe*, Ni*) has been measured as a function of the atomic alignment in the collision frame. The selectivity of the atomic orbital alignment of Ar ((3)P(2), M(J) = 2) (rank 2 moment, a(2)) is found to be opposite for the two reaction systems; the Fe(CO)(5) reaction is favorable at the Π configuration (positive a(2)), while the Ni(CO)(4) reaction is favorable at the Σ configuration (negative a(2)). Moreover, a significant spin alignment effect (rank 4 moment, a(4)) is recognized only in the Ni(CO)(4) reaction. The atomic alignment effect turns out to be essentially different between the two reaction systems; the Fe(CO)(5) reaction is controlled by the configuration of the half-filled 3p atomic orbital of Ar ((3)P(2)) in the collision frame (L dependence), whereas the Ni(CO)(4) reaction is controlled by the configuration of the total angular moment J (including spin) of Ar ((3)P(2)) in the collision frame (J dependence). As the origin of J dependence observed only in the Ni(CO)(4) reaction, the correlation (and/or the interference) between two electron exchange processes via the electron rearrangements is proposed.     

Synthesis, molecular structure and properties of the [H6-nNi30C4(CO)34(CdCl)2]n- (n=3-6) bimetallic carbide carbonyl cluster: a model for the growth of noncompact interstitial metal carbides

Reaction of the [Ni(9)C(CO)(17)](2-) dianion with CdCl(2)2.5 H(2)O in THF affords the novel bimetallic Ni--Cd carbide carbonyl clusters [H(6-n)Ni(30)C(4)(CO)(34)(micro(5)-CdCl)(2)](n-) (n=3-6), which undergo several protonation-deprotonation equilibria in solution depending on the basicity of the solvent or upon addition of acids or bases. Although the occurrence in solution of these equilibria complicates the pertinent electrochemical studies on their electron-transfer activity, they clearly indicate that the clusters [H(6-n)Ni(30)C(4)(CO)(34)(micro(5)-CdCl)(2)](n-) (n=3-6), as well as the structurally related [H(6-n)Ni(34)C(4)(CO)(38)](n-) (n=4-6), undergo reversible or partially reversible redox processes and provide circumstantial and unambiguous evidence for the presence of hydrides for n=3, 4 and 5. Three of the [H(6-n)Ni(30)C(4)(CO)(34)(micro(5)-CdCl)(2)](n-) anions (n=4-6) have been structurally characterized in their [NMe(3)(CH(2)Ph)](4)[H(2)Ni(30)C(4)(CO)(34)(CdCl)(2)]2 COMe(2), [NEt(4)](5)[HNi(30)C(4)(CO)(34)(CdCl)(2)]2 MeCN and [NMe(4)](6)[Ni(30)C(4)(CO)(34)(CdCl)(2)]6 MeCN salts, respectively. All three anions display almost identical geometries and bonding parameters, probably because charge effects are minimized by delocalization over such a large metal carbonyl anion. Moreover, the Ni(30)C(4) core in these Ni-Cd carbide clusters is identical within experimental error to those present in the [HNi(34)C(4)(CO)(38)](5-) and [Ni(35)C(4)(CO)(39)](6-) species, suggesting that the stepwise assembly of their nickel carbide cores may represent a general pathway of growth of nickel polycarbide clusters. The fact that the [H(6-n)Ni(30)C(4)(CO)(34)(micro(5)-CdCl)(2)](n-)(n=4-6) anions display two valence electrons more than the structurally related [H(6-n)Ni(34)C(4)(CO)(38)](n-) (n=4-6) species has been rationalized by extended Hückel molecular orbital (EHMO) analysis.     

Three-dimensional pillar-layered copper(II) metal-organic framework with immobilized functional OH groups on pore surfaces for highly selective CO2/CH4 and C2H2/CH4 gas sorption at room temperature

A new three-dimensional microporous metal-organic framework Cu(BDC-OH)(4,4'-bipy)·G(x) (UTSA-15; H(2)BDC-OH = 2-hydroxy-benzenedicarboxylic acid, 4,4'-bipy =4,4'-bipyridine, G = guest molecules) with functional -OH groups on the pore surfaces was solvothermally synthesized and structurally characterized. UTSA-15 features a three-dimensional structure having 2D intercrossed channels of about 4.1 × 7.8 and 3.7 × 5.1 ?(2), respectively. The small pores and the functional -OH groups on the pore surfaces within the activated UTSA-15a have enabled their strong interactions with CO(2) and C(2)H(2) which have been revealed in their large adsorption enthalpies of 39.5 and 40.6 kJ/mol, respectively, highlighting UTSA-15a as the highly selective microporous metal-organic framework for the CO(2)/CH(4) and C(2)H(2)/CH(4) gas separation with separation selectivity of 24.2 and 55.6, respectively, at 296 K.     

High-pressure in situ 129Xe NMR spectroscopy and computer simulations of breathing transitions in the metal-organic framework Ni2(2,6-ndc)2(dabco) (DUT-8(Ni))

Recently, we have described the metal-organic framework Ni(2)(2,6-ndc)(2)(dabco), denoted as DUT-8(Ni) (1) (DUT = Dresden University of Technology, 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicyclo[2.2.2]octane). Upon adsorption of molecules such as nitrogen and xenon, this material exhibits a pronounced gate-pressure effect which is accompanied by a large change of the specific volume. Here, we describe the use of high-pressure in situ (129)Xe NMR spectroscopy, i.e., the NMR spectroscopic measurements of xenon adsorption/desorption isotherms and isobars, to characterize this effect. It appears that the pore system of DUT-8(Ni) takes up xenon until a liquid-like state is reached. Deeper insight into the interactions between the host DUT-8(Ni) and the guest atom xenon is gained from ab initio molecular dynamics (MD) simulations. van der Waals interactions are included for the first time in these calculations on a metal-organic framework compound. MD simulations allow the identification of preferred adsorption sites for xenon as well as insight into the breathing effect at a molecular scale. Grand canonical Monte Carlo (GCMC) simulations have been performed in order to simulate adsorption isotherms. Furthermore, the favorable influence of a sample pretreatment using solvent exchange and drying with supercritical CO(2) as well as the influence of repeated pore opening/closure processes, i.e., the "aging behavior" of the compound, can be visualized by (129)Xe NMR spectroscopy.