Conversion from Heterometallic to Homometallic Metal–Organic Frameworks

Two new heterometallic metal–organic frameworks (MOFs), LnZnTPO 1 and 2 , and two homometallic MOFs, LnTPO 3 and 4 (Ln=Eu for 1 and 3 , and Tb for 2 and 4 ; H₃TPO=tris(4-carboxyphenyl)phosphine oxide) were synthesized, and their structures and properties were analyzed. They were prepared by solvothermal reaction of the C₃-symmetric ligand H₃TPO with the corresponding metal ion(s) (a mixture of Ln³⁺ and Zn²⁺ for 1 and 2 , and Ln³⁺ alone for 3 and 4 ). Single-crystal XRD (SXRD) analysis revealed that 1 and 3 are isostructural to 2 and 4 , respectively. TGA showed that the framework is thermally stable up to about 400 °C for 1 and 2 , and about 450 °C for 3 and 4 . PXRD analysis showed their pore-structure distortions without noticeable framework–structure changes during drying processes. The shapes of gas sorption isotherms for 1 and 3 are almost identical to those for 2 and 4 , respectively. Solvothermal immersion of 1 and 2 in Tb³⁺ and Eu³⁺ solutions resulted in the framework metal-ion exchange affording 4 and 3 , respectively, as confirmed by photoluminescence (PL), PXRD, IR, inductively coupled plasma atomic emission spectroscopy (ICP-AES), and energy-dispersive X-ray (EDX) analyses.     

Bivariate Metal–Organic Frameworks with Tunable Spin-Crossover Properties

In this work, pyrazine ( A ), aminopyrazine ( B ), quinoxaline ( C ), and 5,6,7,8-tetrahydroquinoxaline ( D ) have been screened out among a large number of pyrazine derivatives to construct Hofmann-type metal–organic frameworks (MOFs) Fe(L)[M(CN)₄] (M=Pt, Pd) with similar 3D pillared-layer structures. X-ray single-crystal diffraction reveals that the alternate linkage between M and Fe^II ions through cyano bridges forms the 2D extended metal cyanide sheets, and ligands A – D acted as vertical columns to connect the 2D sheets to give 3D pillared-layer structures. Subsequently, a series of bivariate MOFs were constructed by pairwise combination of the four ligands A–D , which were confirmed by ¹H NMR, PXRD, FTIR, and Raman spectroscopy. The results demonstrated that ligand size and crystallization rate play a dominant role in constructing bivariate Hofmann-type MOFs. More importantly, the spin-crossover (SCO) properties of the bivariate MOFs can be finely tuned by adjusting the proportion of the two pillared ligands in the 3D Hofmann-type structures. Remarkably, the spin transition temperatures, T_c↑ and T_c↓ of Fe( A )_x( B )_1−x[Pt(CN)₄] (x=0 to 1) can be adjusted from 239 to 254 K and from 248 to 284 K, respectively. Meanwhile, the width of the hysteresis loops can be widened from 9 to 30 K. Changing Pt to Pd, the hysteresis loops of Fe( A )_x( B )_1−x[Pd(CN)₄] can be tuned from 9 (T_c↑=215 K, T_c↓=206 K) to 24 K (T_c↑=300 K, T_c↓=276 K). This research provides wider implications in the development of advanced bistable materials, especially in precisely regulating SCO properties.     

Multi-shelled Hollow Metal–Organic Frameworks

Hollow metal–organic frameworks (MOFs) are promising materials with sophisticated structures, such as multiple shells, that cannot only enhance the properties of MOFs but also endow them with new functions. Herein, we show a rational strategy to fabricate multi-shelled hollow chromium (III) terephthalate MOFs (MIL-101) with single-crystalline shells through step-by-step crystal growth and subsequent etching processes. This strategy relies on the creation of inhomogeneous MOF crystals in which the outer layer is chemically more robust than the inner layer and can be selectively etched by acetic acid. The regulation of MOF nucleation and crystallization allows the tailoring of the cavity size and shell thickness of each layer. The resultant multi-shelled hollow MIL-101 crystals show significantly enhanced catalytic activity during styrene oxidation. The insight gained from this systematic study will aid in the rational design and synthesis of other multi-shelled hollow structures and the further expansion of their applications.     

Metal–Covalent Organic Frameworks (MCOFs): A Bridge Between Metal–Organic Frameworks and Covalent Organic Frameworks

Many sophisticated chemical and physical properties of porous materials strongly rely on the presence of the metal ions within the structures. Whereas homogeneous distribution of metals is conveniently realized in metal–organic frameworks (MOFs), the limited stability potentially restricts their practical implementation. From that perspective, the development of metal–covalent organic frameworks (MCOFs) may address these shortcomings by incorporating active metal species atop highly stable COF backbones. This Minireview highlights examples of MCOFs that tackle important issues from their design, synthesis, characterization to cutting-edge applications.     

Alkali Phosphonate Metal–Organic Frameworks

A new family of porous metal–organic frameworks (MOFs), namely alkali phosphonate MOFs, is reported. [Na₂Cu(H₄TPPA)] ⋅ (NH₂(CH₃)₂)₂ ( GTUB-1 ) was synthesized using the tetratopic 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin ( H₈-TPPA ) linker with planar X-shaped geometrical core. GTUB-1 is composed of rectangular void channels with BET surface area of 697 m² g⁻¹. GTUB-1 exhibits exceptional thermal stability. The toxicity analysis of the ( H₈-TPPA ) linker indicates that it is well tolerated by an intestinal cell line, suggesting its suitability for creating phosphonate MOFs for biological applications.     

Metal–Organic Frameworks as Electrocatalysts

Transition metal complexes are well-known homogeneous electrocatalysts. In this regard, metal–organic frameworks (MOFs) can be considered as an ensemble of transition metal complexes ordered in a periodic arrangement. In addition, MOFs have several additional positive structural features that make them suitable for electrocatalysis, including large surface area, high porosity, and high content of accessible transition metal with exchangeable coordination positions. The present review describes the current state in the use of MOFs as electrocatalysts, both as host of electroactive guests and their direct electrocatalytic activity, particularly in the case of bimetallic MOFs. The field of MOF-derived materials is purposely not covered, focusing on the direct use of MOFs or its composites as electrocatalysts. Special attention has been paid to present strategies to overcome their poor electrical conductivity and limited stability.     

Shaping Microcrystals of Metal–Organic Frameworks by Reaction–Diffusion

When components of a metal–organic framework (MOF) and a crystal growth modulator diffuse through a gel medium, they can form arrays of regularly-spaced precipitation bands containing MOF crystals of different morphologies. With time, slow variations in the local concentrations of the growth modulator cause the crystals to change their shapes, ultimately resulting in unusual concave microcrystallites not available via solution-based methods. The reaction–diffusion and periodic precipitation phenomena 1) extend to various types of MOFs and also MOPs (metal–organic polyhedra), and 2) can be multiplexed to realize within one gel multiple growth conditions, in effect leading to various crystalline phases or polycrystalline formations.     

Modular Customization and Regulation of Metal–Organic Frameworks for Efficient Membrane Separations

Metal–organic frameworks (MOFs) are considered ideal membrane candidates for energy-efficient separations. However, the MOF membrane amount to date is only a drop in the bucket compared to the material collections. The fabrication of an arbitrary MOF membrane exhibiting inherent separation capacity of the material remains a long-standing challenge. Herein, we report a MOF modular customization strategy by employing four MOFs with diverse structures and physicochemical properties and achieving innovative defect-free membranes for efficient separation validation. Each membrane fully displays the separation potential according to the MOF pore/channel microenvironment, and consequently, an intriguing H₂/CO₂ separation performance sequence is achieved (separation factor of 1656–5.4, H₂ permeance of 964–2745 gas permeation unit). Taking advantage of this strategy, separation performance can be manipulated by a non-destructive modification separately towards the MOF module. This work establishes a universal full-chain demonstration for membrane fabrication-separation validation-microstructure modification and opens an avenue for exclusive customization of membranes for important separations.     

Probing the Water Stability Limits and Degradation Pathways of Metal–Organic Frameworks

A comprehensive model to describe the water stability of prototypical metal–organic frameworks (MOFs) is derived by combining different types of theoretical and experimental approaches. The results provide an insight into the early stages of water-triggered destabilization of MOFs and allow detailed pathways to be proposed for the degradation of different MOFs under aqueous conditions. The essential elements of the approach are computing the pK_a values of coordinated water molecules and geometry relaxations. Variable-temperature and pH infrared spectroscopy techniques are used to corroborate the main findings. The model developed herein helps to explain stability limits observed for several prototypical MOFs, including MOF-5, HKUST-1, UiO-66, and MIL-101-Cr, in aqueous solutions, and thus, provides an insight into the possible degradation pathways in acidic and basic environments. The formation of a metal hydroxide through the autoprotolysis of metal-coordinated water molecules and the strength of carboxylate–metal interactions are suggested to be two key players that govern stability in basic and acidic media, respectively. The methodology presented herein can effectively guide future efforts, which are especially significant for in silico screening, for developing novel MOFs with enhanced aqueous stability.     

Enhanced Long Persistent Luminescence by Multifold Interpenetration in Metal–Organic Frameworks

Metal–organic frameworks (MOFs) with long persistent luminescence (LPL) have attracted widespread attention due to potential applications in displays, anticounterfeiting, and so on. However, MOFs often have large pore size, which restricts the formation of efficient inter- and intramolecular interactions to realize LPL. Herein, a new approach to achieving LPL in MOFs by multifold interpenetration of discrete frameworks is reported. By comparison between threefold- and twofold-interpenetrating MOFs, it was found that the former, which have higher multiplicity and denser frameworks, can be endowed with enhanced inter- and intramolecular interactions, and thus enhanced LPL is obtained. Meanwhile, metal-cluster and heavy-halogen effects could also cause variations in LPL duration and color.     

Nanobundles of Iron Phosphide Fabricated by Direct Phosphorization of Metal–Organic Frameworks as an Efficient Hydrogen-Evolving Electrocatalyst

Transition-metal-based phosphides (TMPs) have been considered as attractive electrocatalysts for water splitting due to their earth-abundance and remarkable catalytic activity. As a representative type of precursors, metal-organic frameworks (MOFs) provide ideal plateaus for the design of nanostructured TMPs. In this work, the hierarchically structured iron phosphide nanobundles (FeP-500) were fabricated by one-step phosphorization of an iron-based MOF (MET(Fe)) precursor. The derived FeP-500 nanobundles were constructed by quasi-paralleled one-dimensional nanorods with uneven surface, which provided channels for electrolyte penetration, mass transport, and effective exposure of active sites during the water-splitting process. With the addition of conductive Super P, the obtained FeP-500-S exhibited a good electrocatalytic performance towards the hydrogen evolution reaction in alkaline electrolyte (1 mol L⁻¹ KOH). Furthermore, to investigate the influence of secondary metal doping, a series of isoreticular MOF precursors and bimetallic TMPs were fabricated. The results indicated that the catalytic performance is structure dominated.     

Effect of the Metal within Regioisomeric Paddle-Wheel-Type Metal–Organic Frameworks

The effect of metal on the degree of flexibility upon evacuation of metal–organic frameworks (MOFs) has been revealed with positional control of the organic functionalities. Although Co-, Cu-, and Zn-based DMOFs (DMOF = DABCO MOF, DABCO = 1,4-diazabicyclo[2.2.2]octane) with ortho-ligands (2,3-NH₂Cl) have frameworks that are inflexible upon evacuation, MOFs with para-ligands (2,5-NH₂Cl) showed different N₂ uptake amounts after evacuation by metal exchange. Considering that the structural analyses were not fully sufficiently different to explain the drastic changes in N₂ adsorption after evacuation, quantum chemical simulation was explored. A new index (η) was defined to quantify the regularity around the metal based on differences in the oxygen-metal-oxygen angles. Within 2,5-NH₂Cl, the η value becomes larger as the metal are varied from Co to Zn. A large η value means that the structures around the metal center are less ordered. These results can be used to explain flexibility changes upon evacuation by altering the metal cation in this regioisomeric system.     

Crystal-Growth-Dominated Fabrication of Metal–Organic Frameworks with Orderly Distributed Hierarchical Porosity

Constructing architectures with hierarchical porosity has been widely considered as the most efficient way to bypass the problems related to slow mass transfer and inaccessibility of internal space in MOFs. Now, a crystal-growth-dominated strategy is proposed to fabricate hierarchically porous MOFs (HP-MOFs). When the crystal growth is dominated by the monomer attachment, the aggregation of nonionic surfactant or polymer can be easily captured and released during the crystal growth process, resulting in the formation and ordering hierarchical pores along the radial direction. Owing to the accelerated mass diffusion and more exposed active sites of this design, HP-MOFs exhibited an enhanced catalytic efficiency in styrene oxidation.     

Aqueous Flow Reactor and Vapour-Assisted Synthesis of Aluminium Dicarboxylate Metal–Organic Frameworks with Tuneable Water Sorption Properties

Energy-efficient indoors temperature and humidity control can be realised by using the reversible adsorption and desorption of water in porous materials. Stable microporous aluminium-based metal–organic frameworks (MOFs) present promising water sorption properties for this goal. The development of synthesis routes that make use of available and affordable building blocks and avoid the use of organic solvents is crucial to advance this field. In this work, two scalable synthesis routes under mild reaction conditions were developed for aluminium-based MOFs: (1) in aqueous solutions using a continuous-flow reactor and (2) through the vapour-assisted conversion of solid precursors. Fumaric acid, its methylated analogue mesaconic acid, as well as mixtures of the two were used as linkers to obtain polymorph materials with tuneable water sorption properties. The synthesis conditions determine the crystal structure and either the MIL-53 or MIL-68 type structure with square-grid or kagome-grid topology, respectively, is formed. Fine-tuning resulted in new MOF materials thus far inaccessible through conventional synthesis routes. Furthermore, by varying the linker ratio, the water sorption properties can be continuously adjusted while retaining the sigmoidal isotherm shape advantageous for heat transformation and room climatisation applications.     

Coordination Defect-Induced Frustrated Lewis Pairs in Polyoxo-metalate-Based Metal–Organic Frameworks for Efficient Catalytic Hydrogenation

Precise control of the structure and spatial distance of Lewis acid (LA) and Lewis base (LB) sites in a porous system to construct efficient solid frustrated Lewis pair (FLP) catalyst is vital for industrial application but remains challenging. Herein, we constructed FLP sites in a polyoxometalate (POM)-based metal–organic framework (MOF) by introducing coordination-defect metal nodes (LA) and surface-basic POM with abundant oxygen (LB). The well-defined and unique spatial conformation of the defective POM-based MOF ensure that the distance between LA and LB is at ~4.3 Å, a suitable distance to activate H₂. This FLP catalyst can heterolytically dissociate H₂ into active H^δ−, thus exhibiting high activity in hydrogenation, which is 55 and 2.7 times as high as that of defect-free POM-based MOF and defective MOF without POM, respectively. This work provides a new avenue toward precise design multi-site catalyst to achieve specific activation of target substrate for synergistic catalysis.     

Photoinduced Nonlinear Contraction Behavior in Metal–Organic Frameworks

The photoinduced dynamic behavior of flexible materials has received considerable attention for potential applications, such as in data storage or as smart optical devices and molecular mechanical actuators. Until now, precisely controlling expansion and contraction with light has remained a challenge. Unraveling the detailed mechanisms of photoinduced structural transformations remains a critical step necessary to understand the molecular architecture necessary for the design of sensitive photomechanical actuators. Herein, a two-dimensional flexible metal–organic framework [Zn₂(bdc)₂(3-CH₃-spy)₂]⋅H₂O ( Zn₂-1 ; H₂bdc=1,4-benzenedicaboxylic acid; 3-CH₃-spy=3-methylstyrylpyridine) with a positive volumetric thermal expansion coefficient of +78.78×10⁻⁶ K⁻¹ is reported. Upon light irradiation at different wavelengths, the MOF underwent a [2+2] cycloaddition, which afforded a family of isomeric, three-dimensional MOFs ( Zn₂-2 n , n=a–d) in a single-crystal-to-single-crystal (SCSC) manner. An unprecedented phenomenon, that is, photoinduced nonlinear contraction (PINC), was observed during this conversion. The PINC is caused by conformational changes in the 3-CH₃-spy and bdc²⁻ ligands, the bending of metal–ligand bonds, and the local distortion of the paddle-wheel SBUs. The formation of a “wrinkle morphology” on the crystal surface after the photoreaction was observed by AFM. This PINC behavior can broaden the studies on materials expansion and offer a photodriven approach for the future design of supersensitive photomechanical actuators.     

Metal-Mediated Directional Capping of Rod-Packing Metal–Organic Frameworks

Two new rod-packing metal–organic frameworks (RPMOF) are constructed by regulating the in situ formation of the capping agent. In CPM-s7, carboxylate linkers extend 1D manganese-oxide chains in four additional directions, forming 3D RPMOF. The substitution of Mn²⁺ with a stronger Lewis acidic Co²⁺, leads to an acceleration of the hydrolysis-prone sulfonate linker, resulting in presence of sulfate ions to reduce two out of the four carboxylate-extending directions, and thus forming a new 2D rod-packing CPM-s8. Density functional theory calculations and magnetization measurements reveal ferrimagnetic ordering of CPM-s8, signifying the potential of exploring 2D RPMOF for effective low-dimensional magnetic materials.     

Metal–Organic Frameworks for the Exploitation of Distance between Active Sites in Efficient Photocatalysis

Discoveries of the accurate spatial arrangement of active sites in biological systems and cooperation between them for high catalytic efficiency are two major events in biology. However, precise tuning of these aspects is largely missing in the design of artificial catalysts. Here, a series of metal–organic frameworks (MOFs) were used, not only to overcome the limit of distance between active sites in bio-systems, but also to unveil the critical role of this distance for efficient catalysis. A linear correlation was established between photocatalytic activity and the reciprocal of inter active-site distance; a smaller distance led to higher activity. Vacancies created at selected crystallographic positions of MOFs promoted their photocatalytic efficiency. MOF-525-J33 with 15.6 Å inter active-site distance and 33 % vacancies exhibited unprecedented high turnover frequency of 29.5 h⁻¹ in visible-light-driven acceptorless dehydrogenation of tetrahydroquinoline at room temperature.