Framework-Topology-Controlled Singlet Fission in Metal-Organic Frameworks.

Singlet fission (SF) has been explored as a viable route to improve photovoltaic performance by producing more excitons. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron superexchange to generate triplet pairs. However, strongly coupled chromophores often form excimers that can serve as an SF intermediate or a low-energy trap site. The succeeding decoherence process, however, requires an optimum electronic coupling to facilitate the isolation of triplet production from the initially prepared correlated triplet pair. Conformational flexibility and dielectric modulation can provide a means to tune the SF mechanism and efficiency by modulating the interchromophoric electronic interaction. Such a strategy cannot be easily adopted in densely stacked traditional organic solids. Here, we show that the assembly of the SF-active chromophores around well-defined pores of solution-stable metal-organic frameworks (MOFs) can be a great platform for a modular SF process. A series of three new MOFs, built out from 9,10-bis(ethynylenephenyl)anthracene-derived struts, show a topology-defined packing density and conformational flexibility of the anthracene core to dictate the SF mechanism. Various steady-state and transient spectroscopic data suggest that the initially prepared singlet population can prefer either an excimer-mediated SF or a direct SF (both through a virtual charge-transfer (CT) state). These solution-stable frameworks offer the tunability of the dielectric environment to facilitate the SF process by stabilizing the CT state. Given that MOFs are a great platform for various photophysical and photochemical developments, generating a large population of long-lived triplets can expand their utilities in various photon energy conversion schemes.

Triplet Generation Through Singlet Fission in Metal-Organic Framework: An Alternative Route to Inefficient Singlet-Triplet Intersystem Crossing.

High quantum yield triplets, populated by initially prepared excited singlets, are desired for various energy conversion schemes in solid working compositions like porous MOFs. However, a large disparity in the distribution of the excitonic center of mass, singlet-triplet intersystem crossing (ISC) in such assemblies is inhibited, so much so that a carboxy-coordinated zirconium heavy metal ion cannot effectively facilitate the ISC through spin-orbit coupling. Circumventing this sluggish ISC, singlet fission (SF) is explored as a viable route to generating triplets in solution-stable MOFs. Efficient SF is achieved through a high degree of interchromophoric coupling that facilitates electron super-exchange to generate triplet pairs. Here we show that a predesigned chromophoric linker with extremely poor ISC efficiency (kISC ) but E S 1 ≥ 2 E T 1 ${{E}_{{S}_{1}}\ge {2E}_{{T}_{1}}}$ form triplets in MOF in contrast to the frameworks that are built from linkers with sizable kISC but E S 1 ≤ 2 E T 1 ${{E}_{{S}_{1}}\le {2E}_{{T}_{1}}}$ . This work opens a new photophysical and photochemical avenue in MOF chemistry and utility in energy conversion schemes.

Metal-Carbodithioate-Based 3D Semiconducting Metal-Organic Framework: Porous Optoelectronic Material for Energy Conversion.

Solar energy conversion requires the working compositions to generate photoinduced charges with high potential and the ability to deliver charges to the catalytic sites and/or external electrode. These two properties are typically at odds with each other and call for new molecular materials with sufficient conjugation to improve charge conductivity but not as much conjugation as to overly compromise the optical band gap. In this work, we developed a semiconducting metal-organic framework (MOF) prepared explicitly through metal-carbodithioate "(-CS2)nM" linkage chemistry, entailing augmented metal-linker electronic communication. The stronger ligand field and higher covalent character of metal-carbodithioate linkages─when combined with spirofluorene-derived organic struts and nickel(II) ion-based nodes─provided a stable, semiconducting 3D-porous MOF, Spiro-CS2Ni. This MOF lacks long-range ordering and is defined by a flexible structure with non-aggregated building units, as suggested by reverse Monte Carlo simulations of the pair distribution function obtained from total scattering experiments. The solvent-removed "closed pore" material recorded a Brunauer-Emmett-Teller area of ∼400 m2/g, where the "open pore" form possesses 90 wt % solvent-accessible porosity. Electrochemical measurements suggest that Spiro-CS2Ni possesses a band gap of 1.57 eV (σ = 10-7 S/cm at -1.3 V bias potential), which can be further improved by manipulating the d-electron configuration through an axial coordination (ligand/substrate), the latter of which indicates usefulness as an electrocatalyst and/or a photoelectrocatalyst (upon substrate binding). Transient-absorption spectroscopy reveals a long-lived photo-generated charge-transfer state (τCR = 6.5 µs) capable of chemical transformation under a biased voltage. Spiro-CS2Ni can endure a compelling range of pH (1-12 for weeks) and hours of electrochemical and photoelectrochemical conditions in the presence of water and organic acids. We believe this work provides crucial design principles for low-density, porous, light-energy-conversion materials.

Post-Synthetic Cyano-ferrate(II) Functionalization of a Metal-Organic Framework, NU-1000.

Starting with ferrocyanide ions in acidic aqueous solution, cyano-ferrate(II) species are post-synthetically grafted to the nodes of a mesoporous zirconium-based MOF, NU-1000. As indicated by single-crystal X-ray crystallography, grafting occurs by substitution of cyanide ligands by node-based hydroxo and oxo ligands rather than by substitution of node aqua ligands by cyanide ligands as bridges between Fe(II) and Zr(IV). The installed moieties yield a broad absorption band that is tentatively ascribed to iron-to-zirconium charge transfer. Consistent with Fe(III/II) redox activity, a modest fraction of the installed iron complexes are directly electrochemically addressable.

Synthetic Access to a Framework-Stabilized and Fully Sulfided Analogue of an Anderson Polyoxometalate that is Catalytically Competent for Reduction Reactions.

Polyoxometalates (POMs) featuring 7, 12, 18, or more redox-accessible transition metal ions are ubiquitous as selective catalysts, especially for oxidation reactions. The corresponding synthetic and catalytic chemistry of stable, discrete, capping-ligand-free polythiometalates (PTMs), which could be especially attractive for reduction reactions, is much less well developed. Among the challenges are the propensity of PTMs to agglomerate and the tendency for agglomeration to block reactant access of catalyst active sites. Nevertheless, the pervasive presence of transition metal sulfur clusters metalloenzymes or cofactors that catalyze reduction reactions and the justifiable proliferation of studies of two-dimensional (2D) metal-chalcogenides as reduction catalysts point to the promise of well-defined and controllable PTMs as reduction catalysts. Here, we report the fabrication of agglomeration-immune, reactant-accessible, capping-ligand-free CoIIMo6IVS24n- clusters as periodic arrays in a water-stable, hierarchically porous Zr-metal-organic framework (MOF; NU1K) by first installing a disk-like Anderson polyoxometalate, CoIIIMo6VIO24m-, in size-matched micropores where the siting is established via difference electron density (DED) X-ray diffraction (XRD) experiments. Flowing H2S, while heating, reduces molybdenum(VI) ions to Mo(IV) and quantitatively replaces oxygen anions with sulfur anions (S2-, HS-, S22-). DED maps show that MOF-templated POM-to-PTM conversion leaves clusters individually isolated in open-channel-connected micropores. The structure of the immobilized cluster as determined, in part, by X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS) analysis, and pair distribution function (PDF) analysis of total X-ray scattering agrees well with the theoretically simulated structure. PTM@MOF displays both electrocatalytic and photocatalytic competency for hydrogen evolution. Nevertheless, the initially installed PTM appears to be a precatalyst, gaining competency only after the loss of ∼3 to 6 sulfurs and exposure to hydride-forming metal ions.

Noncovalent Surface Modification of Metal-Organic Frameworks: Unscrambling Adsorption Properties via Isothermal Titration Calorimetry.

Despite the importance of noncovalent interactions in the utilization of metal-organic frameworks (MOFs), using these interactions to functionalize MOFs has rarely been explored. The ease of functionalization and potential for surface-selective functionalization makes modification via noncovalent interactions promising for the creation of porous photocatalytic assemblies. Using isothermal titration calorimetry, photoluminescence measurements, and desorption experiments, we have explored the nature and magnitude of the interactions of [Ru(bpy)2(bpy-R)]2+-functionalized dyes with the surface of MIL-96, where R = C3, C8, C12, and C18 alkyl chains of either straight-chain or cyclic conformations. The orientation of the dyes appears to be flat against the surface with respect to the long alkyl chains, and the surface concentration approaches a monolayer at high initial concentrations of dye. Strangely, the dodecyl-functionalized dye, despite having a smaller interaction energy and larger footprint than either octyl-functionalized dye, achieves the highest maximum surface concentration. Based on photoluminescence spectra, desorption experiments, and ITC data, we believe this is due to the core of the dye being lifted from the surface as the chain length increases. Our understanding of these interactions is important for further utilization of this method for the functionalization of the internal and external surface areas of MOFs.

Direct Observation of Modulated Radical Spin States in Metal-Organic Frameworks by Controlled Flexibility.

Owing to their switchable spin states and dynamic electronic character, organic-based radical species have been invoked in phenomena unique to a variety of fields. When incorporated in solid state materials, generation of organic radicals proves challenging due to aggregation. Metal-organic frameworks (MOFs) are promising candidates for immobilization and stabilization of organic radicals because of the tunable spatial arrangement of organic linkers and metal nodes, which sequesters the reactive species. Herein, a flexible, redox-active tetracarboxylic acid linker bearing two imidazole units was chosen to construct a new Zr6-MOF, NU-910, with scu topology. By exploiting the structural flexibility of NU-910, we successfully modulate the dynamics between an isolated organic radical species and an organic radical π-dimer species in the MOF system. Single-crystal X-ray diffraction analysis reveals that through solvent exchange from N,N-diethylformamide to acetone, NU-910 undergoes a structural contraction with interlinker distances decreasing from 8.32 Å to 3.20 Å at 100 K. Organic radical species on the bridging linkers are generated via UV light irradiation. Direct observation of temperature-induced spin switches from an isolated radical species to a magnetically silent radical π-dimer in NU-910 after irradiation in the solid state was achieved via variable-temperature single-crystal X-ray diffraction and variable-temperature electron paramagnetic resonance spectroscopy. Ultraviolet-visible-near infrared spectroscopy and density functional theory calculations further substantiated the formation of a radical cation π-dimer upon irradiation. This work demonstrates the potential of using flexible MOFs as a platform to modulate radical spin states in the solid phase.

Understanding Diffusional Charge Transport within a Pyrene-Based Hydrogen-Bonded Organic Framework.

Electrochemically active hydrogen-bonded organic frameworks (HOFs) offer opportunities to study charge transport in supramolecular systems where the rate of movement of charges is dependent on weak electronic coupling between individual components. Here, we used potential-step chronoamperometric measurements on electrochemically active, drop-cast HOF-102 films to estimate both redox-hopping-based apparent diffusion coefficients for charge transport and rate constants for linker-to-linker charge transfer (hole transfer) in the mesoporous two-dimensional (2D) plane created by interlinker hydrogen bonding. Also present are one-dimensional columns formed by stacking pyrene units. However, because the HOF-102 crystallites containing these columns are oriented parallel to an underlying electrode, dynamics of charge transport (hole-transport) along the column axis, in contrast to the plane, are not directly probed by the electrochemical measurements. Furthermore, we employed electrochemical impedance spectroscopy to measure the electrical conductivity of the as-deposited films biased at various potentials. We found that both the neutral/singly oxidized and the singly oxidized/doubly oxidized pyrene linker redox couples of HOF-102 can engender hopping-based film conductivity within the 2D plane of HOF-102. Consistent with the radical cation and radical dication nature of the singly and doubly oxidized linkers, respectively, HOF-102 films are electrochromic. The measured values of in-plane charge-diffusion coefficients (∼10-10 to 10-11 cm2 s-1) and electrical conductivity (∼10-6 to 10-8 S cm-1) compare favorably with those for related redox-conductive MOFs and suggest that the transport and conductivity parameters for HOF-102 are sufficiently large to support electrocatalysis by subsequently installed catalysts in films─specifically, films of micron or greater thickness, corresponding to the equivalent hundreds of monolayers of closely packed (i.e., face-to-face-packed) pyrene-derivatives, but with solution access (solvent, ion, and reactant access) still readily provided by channels oriented parallel to an underlying planar electrode.

Superradiance and Directional Exciton Migration in Metal-Organic Frameworks.

Crystalline metal-organic frameworks (MOFs) are promising synthetic analogues of photosynthetic light-harvesting complexes (LHCs). The precise assembly of linkers (organic chromophores) around the topology-defined pores offers the evolution of unique photophysical behaviors that are reminiscence of LHCs. These include MOF excited states with photoabsorbed energy that is spatially dispersed over multiple linkers defining the molecular excitons. The multilinker molecular excitons display superradiance─a hallmark of coupled oscillators seen in LHCs─with radiative rate constant (krad) exceeding that of a single linker. Our theoretical model and experimental results on three zirconium MOFs, namely, PCN-222(Zn), NU-1000, and SIU-100, with similar topology but varying linkers suggest that the size of such molecular excitons depends on the electronic symmetry of the linker. This multilinker exciton model effectively predicts the energy transfer rate constant; corresponding single-step exciton hopping time, ranging from a few picoseconds in SIU-100 and NU-1000 to a few hundreds of picoseconds in PCN-222(Zn), matches well with the experimental data. The model also predicts the anisotropy of exciton displacement with preferential migration along the crystallographic c-axis. Overall, these findings establish various missing links defining the exciton size and dynamics in MOF-assembled linkers. The understandings will provide design principles, especially, positioning the catalysts or electrode relative to the linker orientation for low-density solar energy conversion systems.

Photon Upconversion in a Glowing Metal-Organic Framework.

The interaction of low-energy light with matter that leads to the production of high-energy light is known as photon upconversion. This phenomenon is of importance because of its potential applications in optoelectronics, energy harvesting, and the biomedical arena. Herein, we report a pillared-paddlewheel metal-organic framework (MOF), constructed from a tetrakis(4-carboxyphenyl)porphyrin sensitizer and a dipyridyl thiazolothiazole annihilator, designed for efficient triplet-triplet annihilation upconversion (TTA-UC). Single-crystal X-ray diffraction studies reveal that the Zn-metalated sensitizers are coordinated to Zn2 nodes in a paddlewheel fashion, forming 2D sheets, to which are linked annihilators, such that each sensitizer is connected to five of them. The precise arrangements of sensitizers with respect to annihilators, and the high annihilator-to-sensitizer ratio, facilitate Dexter energy transfer. This level of organization in an extended structure leads to a high TTA-UC efficiency of 1.95% (theoretical maximum = 50%) at an excitation power density of 25 mW cm-2.

Modulation of CO2 adsorption in novel pillar-layered MOFs based on carboxylate-pyrazole flexible linker.

Metal-organic frameworks (MOFs) have attracted significant attention as sorbents due to their high surface area, tunable pore volume and pore size, coordinatively unsaturated metal sites, and ability to install desired functional groups by post-synthetic modification. Herein, we report three new MOFs with pillar-paddlewheel structures that have been synthesized solvothermally from the mixture of the carboxylate-pyrazole flexible linker (H2L), 4,4-bipyridine (BPY)/triethylenediamine (DABCO), and Zn(ii)/Cu(ii) ions. The MOFs obtained, namely [ZnII(L)BPY], [CuII(L)BPY], and [CuII(L)DABCO], exhibit two-fold interpenetration and dinuclear paddle-wheel nodes. The Zn(ii)/Cu(ii) cations are coordinated by two equatorial L linkers that result in two-dimensional sheets which in turn are pillared by BPY or DABCO in the perpendicular direction to obtain a neutral three-dimensional framework that shows one-dimensional square channels. The three pillar-layered MOFs were characterized as microporous materials showing high crystalline stability after activation at 120 °C and CO2 adsorption. All MOFs contain uncoordinated Lewis basic pyrazole nitrogen atoms in the framework which have an affinity toward CO2 and hence could potentially serve as CO2 adsorption material. The CO2 uptake capacity was initially enhanced by replacing Zn with Cu and then replacing the pillar, going from BPY to DABCO. Overall, all the MOFs exhibit low isosteric heat (Qst) of adsorption which signifies an advantage due to the energy required for the adsorption and regeneration processes.

Regioselective Functionalization of the Mesoporous Metal-Organic Framework, NU-1000, with Photo-Active Tris-(2,2'-bipyridine)ruthenium(II).

Solvent-assisted ligand incorporation is an excellent method for the post-synthetic functionalization of Zr-based metal-organic frameworks (MOFs), as carboxylate-derivative functionalities readily coordinate to the Zr6 nodes by displacing node-based aqua and terminal hydroxo ligands. In this study, a photocatalytically active ruthenium complex RuII(bpy)2(dcbpy), that is, bis-(2,2'-bipyridine)-(4,4'-dicarboxy-2,2'-bipyridine)ruthenium, was installed in the mono-protonated (carboxylic acid) form within NU-1000 via SALI. Crystallographic information regarding the siting of the ruthenium complex within the MOF pores is obtained by difference envelope density analysis. The ruthenium-functionalized MOF, termed Ru-NU-1000, shows excellent heterogeneous photocatalytic activity for an oxidative amine coupling reaction.

Charge Transport in Zirconium-Based Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are a class of crystalline porous materials characterized by inorganic nodes and multitopic organic linkers. Because of their molecular-scale porosity and periodic intraframework chemical functionality, MOFs are attractive scaffolds for supporting and/or organizing catalysts, photocatalysts, chemical-sensing elements, small enzymes, and numerous other functional-property-imparting, nanometer-scale objects. Notably, these objects can be installed after the synthesis of the MOF, eliminating the need for chemical and thermal compatibility of the objects with the synthesis milieu. Thus, postsynthetically functionalized MOFs can present three-dimensional arrays of high-density, yet well-separated, active sites. Depending on the application and corresponding morphological requirements, MOF materials can be prepared in thin-film form, pelletized form, isolated single-crystal form, polycrystalline powder form, mixed-matrix membrane form, or other forms. For certain applications, most obviously catalytic hydrolysis and electro- or photocatalytic water splitting, but also many others, an additional requirement is water stability. MOFs featuring hexa-zirconium(IV)-oxy nodes satisfy this requirement. For applications involving electrocatalysis, charge storage, photoelectrochemical energy conversion, and chemiresistive sensing, a further requirement is electrical conductivity, as embodied in electron or hole transport. As most MOFs, under most conditions, are electrically insulating, imparting controllable charge-transport behavior is both a chemically intriguing and chemically compelling challenge.Herein, we describe three strategies to render zirconium-based metal-organic frameworks (MOFs) tunably electrically conductive and, therefore, capable of transporting charge on the few nanometers (i.e., several molecular units) to few micrometers (i.e., typical dimensions for MOF microcrystallites) scale. The first strategy centers on redox-hopping between periodically arranged, chemically equivalent sites, essentially repetitive electron (or hole) self-exchange. Zirconium nodes are electrically insulating, but they can function as grafting sites for (a) redox-active inorganic clusters or (b) molecular redox couples. Alternatively, charge hopping based on linker redox properties can be exploited. Marcus's theory of electron transfer has proven useful for understanding/predicting trends in redox-hopping based conductivity, most notably, in accounting for variations as great as 3000-fold depending on the direction of charge propagation through structurally anisotropic MOFs. In MOF environments, propagation of electronic charge via redox hopping is necessarily accompanied by movement of charge-compensating ions. Consequently, rates of redox hopping can depend on both the identity and concentration of ions permeating the MOF. In the context of electrocatalysis, an important goal is to transport electronic charge fast enough to match or exceed the inherent activity of MOF-based or MOF-immobilized catalysts.Bandlike electronic conductivity is the focus of an alternative strategy: one based on the introduction of molecular guests capable of forming donor-acceptor charge transfer complexes with the host framework. Theory again can be applied predictively to alter conductivity. A third strategy similarly emphasizes electronic conductivity, but it makes use of added bridges in the form of molecular oligomers or inorganic clusters that can then be linked to span the length of a MOF crystallite. For all strategies, retention of molecular-scale porosity is emphasized, as this property is key to many applications. Finally, while our focus is on Zr-MOFs, the described approaches clearly are extendable to other MOF compositions, as has already been demonstrated, in part, in studies by others.

Improving Energy Transfer within Metal-Organic Frameworks by Aligning Linker Transition Dipoles along the Framework Axis.

Crystalline metal-organic frameworks (MOFs) can assemble chromophoric molecules into a wide range of spatial arrangements, which are controlled by the MOF topology. Like natural light-harvesting complexes (LHCs), the precise arrangement modulates interchromophoric interactions, in turn determining excitonic behavior and migration dynamics. To unveil the key factors that control efficient exciton displacements within MOFs, we first developed linkers with low electronic symmetry (as defined by large transition dipoles) and then assembled them into MOFs. These linkers possess extended conjugation along one molecular axis, engendering low optical bandgaps and improved oscillator strength for their lowest-energy transition (S0 → S1). This enhances absorption-emission spectral overlap and boosts the efficiency of Förster resonance energy transfer, which was observed experimentally by a sizable decrease in emission quantum yield (QY), accompanied by a faster population decay profile. We find that MOFs that orient these elongated linkers along their asymmetric pore channel, e.g., the hexagonal pores in an xly network, manifested >50% decrease in their emission QY with faster decay profiles relative to their corresponding solution dissolved linkers. This is due to an efficient migration of photogenerated excitons at the crystallite peripheral sites to internal sites, which was facilitated by polarized absorption-emission overlap among the parallelly aligned linkers. In contrast, symmetric MOFs, such as those with sqc-a topological net, orient elongated linkers along two perpendicular crystal axes, which hinders efficient exciton migration. The present study underscores that MOFs are promising to develop artificial LHCs, but that to achieve an efficient exciton displacement, appropriate topology-guided assembly is required to fully realize the true potential of linkers with low electronic symmetry.

A Flexible Interpenetrated Zirconium-Based Metal-Organic Framework with High Affinity toward Ammonia.

Flexible metal-organic frameworks (MOFs) are highly attractive porous crystalline materials presenting structural changes when exposed to external stimuli, the mechanism of which is often difficult to glean, owing to their complex and dynamic nature. Herein, a flexible interpenetrated Zr-MOF, NU-1401, composed of rare 4-connected Zr6 nodes and tetratopic naphthalenediimide (NDI)-based carboxylate linkers, was designed. The intra-framework pore opening deformation and inter-framework motions, when subjected to different solvent molecules, were investigated by single-crystal XRD. The distance and overlap angle between the stacked NDI pairs in the entangled structure could be finely tuned, and the interactions between NDI and solvent molecules led to solvochromism. Furthermore, the presence of electron-deficient NDI units in the linker and acid sites on the node of the interpenetrated porous structure offered high density of adsorption sites for ammonia molecules, resulting in high uptake at low pressures.

Anisotropic Redox Conductivity within a Metal-Organic Framework Material.

Engendering electrical conductivity in otherwise insulating metal-organic framework (MOF) materials is key to rendering these materials fully functional for a range of potential applications, including electrochemical and photo-electrochemical catalysis. Here we report that the platform MOF, NU-1000, can be made electrically conductive via reversible electrochemical oxidation of a fraction of the framework's tetraphenylpyrene linkers, where the basis for conduction is redox hopping. At a microscopic level, redox hopping is akin to electron self-exchange and is describable by Marcus' well-known theory of electron transfer. At a macroscopic level, the hopping behavior leads to diffusive charge transport and is quantifiable as an apparent diffusion coefficient, Dhopping. Theory suggests that the csq topology of NU-1000, together with its characteristic one-dimensional mesopores, will result in direction-dependent, that is, anisotropic, electrical conductivity. Detailed computations suggest that the governing factor is the strength of electronic coupling between pairs of linkers sited in the a,b plane of the MOF versus the mesopore-aligned c axis of the crystal. The notion has been put to the test experimentally by configuring the MOF as an array of selectively oriented, electrode-supported crystallites, where the rodlike crystallites are either oriented largely normal to the electrode (requiring redox hopping along the c direction) or mainly parallel (requiring redox hopping mainly through the a,b plane). The orientations are preselected by preparing MOF films either via interfacial solvothermal synthesis or via electrophoretic deposition. In semiquantitative accord with computational predictions, Dhopping is up to ∼3500 times larger in the c direction than through the a,b plane. In addition to their fundamental significance, the findings have clear implications for the design and optimization of MOFs for electrocatalysis and for other applications that rely upon electrical conductivity.

Torsion Angle Effect on the Activation of UiO Metal-Organic Frameworks.

We present a systematic investigation of the factors influencing the surface area of zirconium-based UiO-type metal-organic frameworks (MOFs), revealing an important relationship between factors including the conformation of the organic linker in the MOF, surface tension of the guest molecules (solvent), and the stability of MOFs toward activation (removal of guest molecules). The results obtained demonstrate how the structure of the linkers forming the isostructural series of UiO MOFs with fcu topology could alter the resistance and stability of the MOF frameworks toward capillary force-driven structural degradation governed by the solvent during activation.

Porosity Dependence of Compression and Lattice Rigidity in Metal-Organic Framework Series.

Porous materials, including metal-organic frameworks (MOFs), are known to undergo structural changes when subjected to applied hydrostatic pressures that are both fundamentally interesting and practically relevant. With the rich structural diversity of MOFs, the development of design rules to better understand and enhance the mechanical stability of MOFs is of paramount importance. In this work, the compressibilities of seven MOFs belonging to two topological families (representing the most comprehensive study of this type to date) were evaluated using in situ synchrotron X-ray powder diffraction of samples within a diamond anvil cell. The judicious selection of these materials, representing widely studied classes of MOFs, provides broadly applicable insight into the rigidity and compression of hybrid materials. An analysis of these data reveals that the bulk modulus depends on several structural parameters (e.g., void fraction and linker length). Furthermore, we find that lattice distortions play a major role in the compression of MOFs. This study is an important step toward developing a predictive model of the structural variables that dictate the compressibility of porous materials.

Stabilization of an Unprecedented Hexanuclear Secondary Building Unit in a Thorium-Based Metal-Organic Framework.

The crystal structures of thorium clusters are important for understanding the formation and transformation mechanisms of actinide species in solution, which can in turns benefit nuclear waste processing and management. However, stabilizing thorium clusters in aqueous solution is quite challenging because of their fast olation and oxolation reactions. Here, we report a thorium-based metal-organic framework, NU-905, with the formula [Th6(µ3-O)2(HCOO)4(H2O)6(TCPP)4] [TCPP = tetrakis(4-carboxyphenyl)porphyrin], synthesized by a solvothermal reaction in N, N-dimethylformamide and water at 120 °C. NU-905 contains a hexanuclear secondary building unit (SBU), [Th6(µ3-O)2(HCOO)4(H2O)6], which has never been reported previously. The SBUs are capped and bridged by the tetratopic linker TCPP to form a three-dimensional network with scu topology. The activated NU-905 exhibits permanent porosity and shows high catalytic activity for the selective photooxidation of a mustard gas simulant.

Oxygen-Assisted Cathodic Deposition of Zeolitic Imidazolate Frameworks with Controlled Thickness.

Processing metal-organic frameworks (MOFs) as films with controllable thickness on a substrate is increasingly crucial for many applications to realize function integration and performance optimization. Herein, we report a facile cathodic deposition process that enables the large-area preparation of uniform films of zeolitic imidazolate frameworks (ZIF-8, ZIF-71, and ZIF-67) with highly tunable thickness ranging from approximately 24 nm to hundreds of nanometers. Importantly, this oxygen-reduction-triggered cathodic deposition does not lead to the plating of reduced metals (Zn and Co). It is also operable cost-effectively in the absence of supporting electrolyte and facilitates the construction of well-defined sub-micrometer-sized heterogeneous structures within ZIF films.