Melt-quenched carboxylate metal-organic framework glasses.

Although carboxylate-based frameworks are commonly used architectures in metal-organic frameworks (MOFs), liquid/glass MOFs have thus far mainly been obtained from azole- or weakly coordinating ligand-based frameworks. This is because strong coordination bonds of carboxylate ligands to metals block the thermal vitrification pathways of carboxylate-based MOFs. In this study, we present the example of carboxylate-based melt-quenched MOF glasses comprising Mg2+ or Mn2+ with an aliphatic carboxylate ligand, adipate. These MOFs have a low melting temperature (Tm) of 284 °C and 238 °C, respectively, compared to zeolitic-imidazolate framework (ZIF) glasses, and superior mechanical properties in terms of hardness and elastic modulus. The low Tm may be attributed to the flexibility and low symmetry of the aliphatic carboxylate ligand, which raises the entropy of fusion (ΔSfus), and the lack of crystal field stabilization energy on metal ions, reducing enthalpy of fusion (ΔHfus). This research will serve as a cornerstone for the integration of numerous carboxylate-based MOFs into MOF glasses.

Computational Prediction of Stacking Mode in Conductive Two-Dimensional Metal-Organic Frameworks: An Exploration of Chemical and Electrical Property Changes.

Conductive two-dimensional metal-organic frameworks (2D MOFs) have attracted interest as they induce strong charge delocalization and improve charge carrier mobility and concentration. However, characterizing their stacking mode depends on expensive and time-consuming experimental measurements. Here, we construct a potential energy surface (PES) map database for 36 2D MOFs using density functional theory (DFT) for the experimentally synthesized and non-synthesized 2D MOFs to predict their stacking mode. The DFT PES results successfully predict the experimentally synthesized stacking mode with an accuracy of 92.9% and explain the coexistence mechanism of dual stacking modes in a single compound. Furthermore, we analyze the chemical (i.e., host-guest interaction) and electrical (i.e., electronic structure) property changes affected by stacking mode. The DFT results show that the host-guest interaction can be enhanced by the transition from AA to AB stacking, taking H2S gas as a case study. The electronic band structure calculation confirms that as AB stacking displacement increases, the in-plane charge transport pathway is reduced while the out-of-plane charge transport pathway is maintained or even increased. These results indicate that there is a trade-off between chemical and electrical properties in accordance with the stacking mode.

Effect of steric hindrance on the interfacial connection of MOF-on-MOF architectures.

MOF-on-MOF is attracting great attention due to its improved and/or synergistic properties not exhibited in a single MOF. In particular, the non-isostructural pairs of MOF-on-MOFs can have great potential induced by large heterogeneity, which enables diverse applications in a wide range of fields. HKUST-1@IRMOF is a fascinating platform because the alteration of the IRMOF pores with bulkier substituent groups on the ligands can provide a more microporous environment. However, the sterically hindered linker can affect the seamless growth at the interface, an important issue in practical research fields. Despite many efforts to reveal the growth of a MOF-on-MOF, there is still a lack of studies on a MOF-on-MOF consisting of a sterically hindered interface. Indeed, the effect of a bulky linker at an interface of HKUST-1@IRMOF, a non-isostructural MOF-on-MOF system, has not yet been reported, and thus, how the interfacial strain affects the interfacial growth remains unknown. In this study, we investigate the effect of an interfacial strain on a chemical connection point in an MOF-on-MOF system through a series of theoretical and synthetic experiments using a HKUST-1@IRMOF system. Our results reveal the importance of the proximity of each coordinating site at a MOF-on-MOF interface as well as lattice parameter matching for an effective secondary growth to achieve a well-connected MOF-on-MOF.

Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks.

Because of their designability and unprecedented synergistic effects, core-shell metal-organic frameworks (MOFs) have been actively examined recently. However, the synthesis of single-crystalline core-shell MOFs is very challenging, and thus a limited number of examples have been reported. Here, we suggest a method of synthesizing single-crystalline HKUST-1@MOF-5 core-shells, which is HKUST-1 at the center of MOF-5. Through the computational algorithm, this pair of MOFs was predicted to have the matched lattice parameters and chemical connection points at the interface. To construct the core-shell structure, we prepared the octahedral- and cubic-shaped HKUST-1 crystals as a core MOF, in which the (111) and (001) facets were mainly exposed, respectively. Via the sequential reaction, the MOF-5 shell was well-grown on the exposed surface, showing a seamless connect interface, which resulted in the successful synthesis of single-crystalline HKUST-1@MOF-5. Their pure phase formation was proved by optical microscopic images and powder X-ray diffraction (PXRD) patterns. This method presents the potential of and insights into the single-crystalline core-shell synthesis with different kinds of MOFs.

Thermodynamic Separation of Hydrogen Isotopes Using Hofmann-Type Metal-Organic Frameworks with High-Density Open Metal Sites.

Hydrogen isotope separation with nanoporous materials is a very challenging yet promising approach. To overcome the limitation of the conventional isotope separation strategy, quantum sieving-based separation using nanoporous materials has been investigated recently. In this study, to see the thermodynamic deuterium separation phenomena attributed to the chemical affinity quantum sieving effect, we examine Hofmann-type metal-organic frameworks (MOFs), Co(pyz)[M(CN)4] (pyz = pyrazine, M = Pd2+, Pt2+, and Ni2+), which have microporosity (4.0 × 3.9 Å2) and an extraordinarily high density of open metal sites (∼9 mmol/cm3). Owing to the preferential adsorption of D2 over H2 at strongly binding open metal sites, the Hofmann-type MOF, Co(pyz)[Pd(CN)4] exhibited a high selectivity (SD2/H2) of 21.7 as well as a large D2 uptake of 10 mmol/g at 25 K. This is the first study of Hofmann-type MOFs to report high selectivity and capacity, both of which are important parameters for the practical application of porous materials toward isotope separation.

Post-synthetic ligand cyclization in metal-organic frameworks through functional group connection with regioisomerism.

A covalent connection between two orthogonal functional groups (-NH2 and -OH) in metal-organic frameworks (MOFs) has been developed. This post-synthetic ligand cyclization (PSLC) was successfully demonstrated to synthesize a benzoxazole-functionalized MOF from a Zr-based UiO-66-2,3-(NH2)(OH) under microwave irradiation. In contrast, the regioisomeric UiO-66-2,5-(NH2)(OH) only produces a non-cyclized formamide-functionalized MOF.

Metal-Organic Frameworks: Special Collection 2020.

MOF2020: This Editorial introduces a special collection of review and original research articles, dedicated to the MOF2020 web conference.

Modulating Energetic Characteristics of Multicomponent 1D Coordination Polymers: Interplay of Metal-Ligand Coordination Modes.

The energetic properties of multicomponent explosive materials can be altered for high detonation capabilities and minimized safety risk by changing their building components. We synthesized energetic coordination polymers (ECPs) using a 5,5'-bis(tetrazole)-1,1'-diolate linker and a N,N-dimethylacetamide (DMA) solvent, together with Cu and Mn metal cations. The new compounds, ECP-1 and ECP-2, contain two different types of 1D chain structures, straight and helical. We have conducted comprehensive studies on these ECP structures, energetic properties, and sensitivity and found excellent insensitivity owing to the long chain-to-chain distances created by the DMA solvent molecules. The results indicate that the metals as well as solvents used are crucial components influencing both the structure and energetic properties.

Non-stackable molecules assemble into porous crystals displaying concerted cavity-changing motions.

With small molecules, it is not easy to create large void spaces. Flat aromatics stack tightly, while flexible chains fold to fill the cavities. As an intuitive design to make open channels inside molecularly constructed solids, we employed propeller-shaped bicyclic triazoles to prepare a series of aromatic-rich three-dimensional (3D) building blocks. This modular approach has no previous example, but is readily applicable to build linear, bent, and branched arrays of non-stackable architectural motifs from existing flat aromatics by single-pot reactions. A letter H-shaped molecule thus prepared self-assembles into porous crystals, the highly unusual stepwise gas sorption behaviour of which prompted in-depth studies. A combination of single-crystal and powder X-ray diffraction analysis revealed multiple polymorphs, and sterically allowed pathways for their reversible interconversions that open and close the pores in response to external stimuli.

Nanocomposite synthesis strategies based on the transformation of well-tailored metal-organic frameworks.

Increasing the complexity of nanomaterials in terms of their structure and chemical composition has attracted significant attention, because it can yield unique scientific outcomes and considerable improvements for practical applications. Various approaches are being developed for the synthesis of nanostructured composites. Coordination polymers (CPs) emerged as new precursors in solid-state reactions for nanomaterials nearly two decades ago; the repetitively arranged inorganic and organic units can facilitate the production of nanoscale particles and porous carbon upon thermal decomposition. Metal-organic frameworks (MOFs), a subgroup of CPs featuring crystalline and porous structures, have subsequently become primary objects of interest in this field, as can be seen by the rapidly increasing number of reports on this topic. However, unique composite materials with increasingly complex nanostructures, which cannot be achieved via conventional methods, have been rarely realised, even though conventional MOF research has enabled the delicate control of structures at the molecular level and extensive applications as templates. In this regard, a comprehensive review of the fabrication strategies of MOF-based precursors and the thermal transformation into functional nanomaterials is provided herein, with a particular emphasis on the recent developments in nanocomposite research. We briefly introduce the roles and capabilities of MOFs in the synthesis of nanomaterials and subsequently discuss diverse synthetic routes for obtaining morphologically or compositionally advanced composite nanomaterials, based on our understanding of the MOF conversion mechanism.

Mechanochemistry as a Reconstruction Tool of Decomposed Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) undergo structural decomposition or phase transformation upon hydration in aqueous media or under harsh conditions, limiting their industrial commercialization. Herein, we present mechanochemical strategies to reconstruct four selected MOFs (MOF-5, MOF-177, UiO-67, and ZIF-65). To verify the effectiveness of this approach, these MOFs were intentionally decomposed in aqueous media and subsequently treated by ball milling under optimized conditions. As confirmed by X-ray diffraction analysis and N2 sorption isotherms, regardless of the MOF degradation pathway, the original structure could be recovered by a tailored mechanochemical reaction. This approach expands the practical applications of MOFs by enabling the regeneration of deteriorated MOFs quickly at a large scale.

Elucidation of Diffusivity of Hydrogen Isotopes in Flexible MOFs by Quasi-Elastic Neutron Scattering.

Kinetic-quantum-sieving-assisted H2 :D2 separation in flexible porous materials is more effective than the currently used energy-intensive cryogenic distillation and girdle-sulfide processes for isotope separation. It is believed that material flexibility results in a pore-breathing phenomenon under the influence of external stimuli, which helps in adjusting the pore size and gives rise to the optimum quantum-sieving phenomenon at each stage of gas separation. However, only a few studies have investigated kinetic-quantum-sieving-assisted isotope separation using flexible porous materials. In addition, no reports are available on the microscopic observation of isotopic molecular transportation during the separation process under dynamic transition. Here, the experimental observation of a significantly faster diffusion of deuterium than hydrogen in a flexible pore structure, even at high temperatures, through quasi-elastic neutron scattering, is reported. Unlike rigid structures, the extracted diffusion dynamics of hydrogen isotopes within flexible frameworks show that the diffusion difference between the isotopes increases with an increase in temperature. Owing to this unique inverse trend, a new strategy is suggested for achieving higher operating temperatures for efficient isotope separation utilizing a flexible metal-organic framework system.

Porous and Nonporous Coordination Polymers Induced by Pseudohalide Ions for Luminescence and Gas Sorption.

The three-dimensional (3D) coordination polymers [Cd(tpmd)(NCX)2]n [X = O (1), S (2), and BH3 (3); tpmd = N,N,N',N'-tetrakis(pyridin-4-yl)methanediamine] have been determined to display their network structures through coordinated anionic ligands. Polymers 1 and 2 show nonporous structures, whereas polymer 3 shows a porous coordination framework. On the basis of the Cd(II) network structures, the 3D coordination polymer [Zn(tpmd)(NCBH3)2]n·nMeOH (4) was self-assembled. In the cases of polymers 1 and 2, pseudohalide ions acted to form nonporous network structures; however, in polymers 3 and 4, NCBH3- helps to construct porous network structures. Polymers 1-4 show strong ultraviolet luminescence emissions, depending on the pseudohalide ions present, compared to the tpmd ligands. Interestingly, coordination polymers 3 and 4 that possess NCBH3- ions exhibit high porosities and gas sorption properties. The polymers appeared to absorb N2, H2, CO2, and CH4. In the case of polymer 4, the structure is almost identical with that of polymer 3, except for the Cd(II) ion. However, polymer 4 has a larger void volume and higher gas absorption ability for N2 gas than polymer 3. For the sorption of gases, polymers 3 and 4 showed similar behaviors.

Specific Isotope-Responsive Breathing Transition in Flexible Metal-Organic Frameworks.

An isotope-selective responsive system based on molecular recognition in porous materials has potential for the storage and purification of isotopic mixtures but is considered unachievable because of the almost identical physicochemical properties of the isotopes. Herein, a unique isotope-responsive breathing transition of the flexible metal-organic framework (MOF), MIL-53(Al), which can selectively recognize and respond to only D2 molecules through a secondary breathing transition, is reported. This novel phenomenon is examined using in situ neutron diffraction experiments under the same conditions for H2 and D2 sorption experiments. This work can guide the development of a novel isotope-selective recognition system and provide opportunities to fabricate flexible MOF systems for energy-efficient purification of the isotopic mixture.

Dual-fixations of europium cations and TEMPO species on metal-organic frameworks for the aerobic oxidation of alcohols.

The efficient and selective aerobic oxidation of alcohols has been investigated with judicious combinations of europium-incorporated and/or TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl)-functionalized zirconium-based porous metal-organic frameworks (MOFs). Although MOFs are well-known catalytic platforms for the aerobic oxidation with radical-functionalities and metal nanoparticles, these systematic approaches involving metal cations and/or radical species introduce numerous interesting aspects for cooperation between metals and TEMPO for the aerobic oxidation of alcohols. The role of TEMPO as the oxidant in the heterogeneous catalytic aerobic oxidation of alcohols was revealed through a series of comparisons between metal-anchored, TEMPO-anchored, and metal and TEMPO-anchored MOF catalysis. The fine tunability of the MOF allowed the homogeneously and doubly functionalized catalysts to undergo organic reactions in the heterogeneous media. In addition, the well-defined and carefully designed heterogeneous molecular catalysts displayed reusability along with better catalytic performance than the homogeneous systems using identical coordinating ligands. The role of metal-cation fixation should be carefully revised to control their coordination and maximize their catalytic activity. Lastly, the metal cation-fixed MOF displayed better substrate tolerance and reaction efficiencies than the TEMPO-anchored MOF or mixture MOF systems.

Surface-Deactivated Core-Shell Metal-Organic Framework by Simple Ligand Exchange for Enhanced Size Discrimination in Aerobic Oxidation of Alcohols.

Metal-organic frameworks (MOFs) are an attractive catalyst support for stable immobilization of the active sites in their scaffold due to the high tunability of organic ligands. The active site-functionalized ligands can be easily employed to construct MOFs as porous heterogeneous catalysts. However, the existence of active sites on the external surfaces as well as internal pores of MOFs seriously impedes the selective reaction in the pore. Herein, through a simple post-synthetic ligand exchange (PSE) method we synthesized surface-deactivated (only core-active) core-shell-type MOF catalysts, which contain 2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) groups on the ligand as active sites for aerobic oxidation of alcohols. The porous but catalytically inactive shell ensured the size-selective permeability by sieving effects and induced all reactions to take place in the pores of the catalytically active core. Because PSE is a facile and universal approach, this can be rapidly applied to a variety of MOF-based catalysts for enhancing reaction selectivity.

Computer-aided discovery of connected metal-organic frameworks.

Composite metal-organic frameworks (MOFs) tend to possess complex interfaces that prevent facile and rational design. Here we present a joint computational/experimental workflow that screens thousands of MOFs and identifies the optimal MOF pairs that can seamlessly connect to one another by taking advantage of the fact that the metal nodes of one MOF can form coordination bonds with the linkers of the second MOF. Six MOF pairs (HKUST-1@MOF-5, HKUST-1@IRMOF-18, UiO-67@HKUST-1, PCN-68@MOF-5, UiO-66@MIL-88B(Fe) and UiO-67@MIL-88C(Fe)) yielded from our theoretical predictions were successfully synthesized, leading to clean single crystalline MOF@MOF, demonstrating the power of our joint workflow. Our work can serve as a starting point to accelerate the discovery of novel MOF composites that can potentially be used for many different applications.

Tuning of the flexibility in metal-organic frameworks based on pendant arm macrocycles.

An isostructural series of flexible metal-organic frameworks based on macrocycles having diverse pendant arms was developed to tune flexibility depending on functional groups. The pendant arms directing into the pores were found to play a key role in imparting different gate-opening behaviours in the threshold pressure and sorption capacity upon interaction with guest molecules.

Coordinated Molecule-Modulated Magnetic Phase with Metamagnetism in Metal-Organic Frameworks.

Most well-known metal-organic frameworks (MOFs) possessing the magnetic Ni2O2(CO2)2 chains, called Ni-MOF-74, have been investigated with regard to magnetic properties at open-metal sites. We present the modulation of their magnetic phase and metamagnetism via imidazole molecule coordination.

Versatile Processing of Metal-Organic Framework-Fluoropolymer Composite Inks with Chemical Resistance and Sensor Applications.

We report a new class of metal-organic framework (MOF) inks with a water-repellent, photocurable fluoropolymer (PFPE) having up to 90 wt % MOF loading. These MOF inks are enabled to process various MOFs through spray coating, pen writing, stencil printing, and molding at room temperature. Upon UV curing, the hydrophobic PFPE matrix efficiently blocks water permeation but allows accessibility of chemicals into the MOF pores, thereby freeing the MOF to perform its unique function. Moreover, by introducing functional MOFs we successfully demonstrated a water-tolerant chemosensor for a class of aromatic pollutants in water and a chemical-resistant thermosensor for visualizing temperature image. This approach would open up innumerable opportunities for those MOFs that are otherwise dormant.