Switchable electrical conductivity in a three-dimensional metal–organic framework via reversible ligand n-doping

Redox-active metal–organic frameworks (MOFs) are promising materials for a number of next-generation technologies, and recent work has shown that redox manipulation can dramatically enhance electrical conductivity in MOFs. However, ligand-based strategies for controlling conductivity remain under-developed, particularly those that make use of reversible redox processes. Here we report the first use of ligand n-doping to engender electrical conductivity in a porous 3D MOF, leading to tunable conductivity values that span over six orders of magnitude. Moreover, this work represents the first example of redox switching leading to reversible conductivity changes in a 3D MOF.

Redox-active ligands are used to reversibly tune electrical conductivity in a porous 3D metal–organic framework (MOF).     

Acid-triggered interlayer sliding of two-dimensional copper(i)–organic frameworks: more metal sites for catalysis

The interlay sliding of two-dimensional (2D) metal–organic and covalent–organic frameworks (MOFs and COFs) affects not only the layout features of the structures, but also the functional output of the materials. However, the control of interlay stacking is the major hurdle that needs to be overcome to construct new functional layer materials. Herein, we report the preparation of a pair of isostructural 2D copper(i) organic frameworks with an eclipsed AA stacking structure, namely JNM-3-AA, and a staggered ABC stacking topology, denoted JNM-3-ABC, by combining the chemistry of MOFs and COFs. The variation of interlayer stacking largely influences their functionality, including porosity (BET surface areas of 695.61 and 34.22 m² g⁻¹ for JNM-3-AA and JNM-3-ABC, respectively), chemical stability, and catalytic activities (less than 10% or ∼86% yield using JNM-3-AA or JNM-3-ABC as catalysts for click reaction, respectively). More interestingly, the structure transformation from JNM-3-ABC to JNM-3-AA is readily achieved by simple addition of trifluoroacetic acid accompanied by the extension of porosities from BET surface areas of 34.22 to 441.22 m² g⁻¹, resulting in in situ acceleration of the adoption rate (removal efficiency increases from ∼10 to 99.9%), which is rarely observed in 2D MOFs and COFs.

The addition of TFA can trigger the interlay sliding of 2D copper(i) organic frameworks prepared by combing the chemistry of MOFs and COFs. The variation of interlay stacking largely affected the porosity, chemical stability and catalytic activities.     

Beyond structural motifs: the frontier of actinide-containing metal–organic frameworks

In this perspective, we feature recent advances in the field of actinide-containing metal–organic frameworks (An-MOFs) with a main focus on their electronic, catalytic, photophysical, and sorption properties. This discussion deviates from a strictly crystallographic analysis of An-MOFs, reported in several reviews, or synthesis of novel structural motifs, and instead delves into the remarkable potential of An-MOFs for evolving the nuclear waste administration sector. Currently, the An-MOF field is dominated by thorium- and uranium-containing structures, with only a few reports on transuranic frameworks. However, some of the reported properties in the field of An-MOFs foreshadow potential implementation of these materials and are the main focus of this report. Thus, this perspective intends to provide a glimpse into the challenges, triumphs, and future directions of An-MOFs in sectors ranging from the traditional realm of gas sorption and separation to recently emerging areas such as electronics and photophysics.

This perspective deviates from exclusively focusing on structural features of actinide-containing metal-organic frameworks and pivots towards their prospect as avant-garde materials with an emphasis on their physicochemical properties.     

Modulated self-assembly of metal–organic frameworks

Exercising fine control over the synthesis of metal–organic frameworks (MOFs) is key to ensuring reproducibility of physical properties such as crystallinity, particle size, morphology, porosity, defectivity, and surface chemistry. The principle of modulated self-assembly – incorporation of modulator molecules into synthetic mixtures – has emerged as the primary means to this end. This perspective article will detail the development of modulated synthesis, focusing primarily on coordination modulation, from a technique initially intended to cap the growth of MOF crystals to one that is now used regularly to enhance crystallinity, control particle size, induce defectivity and select specific phases. The various mechanistic driving forces will be discussed, as well as the influence of modulation on physical properties and how this can facilitate potential applications. Modulation is also increasingly being used to exert kinetic control over self-assembly; examples of phase selection and the development of new protocols to induce this will be provided. Finally, the application of modulated self-assembly to alternative materials will be discussed, and future perspectives on the area given.

This Perspective gives an overview of the modulated self-assembly of MOFs – incorporating additives and alternative precursors into syntheses – focusing on its varying influences on crystallization mechanisms, physical properties, and applications.     

Solid-state NMR spectroscopy: an advancing tool to analyse the structure and properties of metal–organic frameworks

Metal–organic frameworks (MOFs) gain increasing interest due to their outstanding properties like extremely high porosity, structural variability, and various possibilities for functionalization. Their overall structure is usually determined by diffraction techniques. However, diffraction is often not sensitive for subtle local structural changes and ordering effects as well as dynamics and flexibility effects. Solid-state nuclear magnetic resonance (ssNMR) spectroscopy is sensitive for short range interactions and thus complementary to diffraction techniques. Novel methodical advances make ssNMR experiments increasingly suitable to tackle the above mentioned problems and challenges. NMR spectroscopy also allows study of host–guest interactions between the MOF lattice and adsorbed guest species. Understanding the underlying mechanisms and interactions is particularly important with respect to applications such as gas and liquid separation processes, gas storage, and others. Special in situ NMR experiments allow investigation of properties and functions of MOFs under controlled and application-relevant conditions. The present minireview explains the potential of various solid-state and in situ NMR techniques and illustrates their application to MOFs by highlighting selected examples from recent literature.

Metal–organic frameworks (MOFs) gain increasing interest due to their outstanding properties like extremely high porosity, structural variability, and various possibilities for functionalization.     

Direct air capture of CO2via crystal engineering

This article presents a perspective view of the topic of direct air capture (DAC) of carbon dioxide and its role in mitigating climate change, focusing on a promising approach to DAC involving crystal engineering of metal–organic and hydrogen-bonded frameworks. The structures of these crystalline materials can be easily elucidated using X-ray and neutron diffraction methods, thereby allowing for systematic structure–property relationships studies, and precise tuning of their DAC performance.

A perspective view of direct air capture (DAC) of CO₂ and its role in mitigating climate change is presented. The article focuses on a promising approach to DAC involving crystal engineering of metal–organic and hydrogen-bonded frameworks.     

17O NMR spectroscopy of crystalline microporous materials

Microporous materials, containing pores and channels of similar dimensions to small molecules have a range of applications in catalysis, gas storage and separation and in drug delivery. Their complex structure, often containing different types and levels of positional, compositional and temporal disorder, makes structural characterisation challenging, with information on both long-range order and the local environment required to understand the structure–property relationships and improve the future design of functional materials. In principle, ¹⁷O NMR spectroscopy should offer an ideal tool, with oxygen atoms lining the pores of many zeolites and phosphate frameworks, playing a vital role in host–guest chemistry and reactivity, and linking the organic and inorganic components of metal–organic frameworks (MOFs). However, routine study is challenging, primarily as a result of the low natural abundance of this isotope (0.037%), exacerbated by the presence of the quadrupolar interaction that broadens the spectral lines and hinders the extraction of information. In this Perspective, we will highlight the current state-of-the-art for ¹⁷O NMR of microporous materials, focusing in particular on cost-effective and atom-efficient approaches to enrichment, the use of enrichment to explore chemical reactivity, the challenge of spectral interpretation and the approaches used to help this and the information that can be obtained from NMR spectra. Finally, we will turn to the remaining challenges, including further improving sensitivity, the high-throughput generation of multiple structural models for computational study and the possibility of in situ and in operando measurements, and give a personal perspective on how these required improvements can be used to help solve important problems in microporous materials chemistry.

Cost-effective and atom-efficient isotopic enrichment enables ¹⁷O NMR spectroscopy of microporous materials to be used to probe local structure and disorder and to explore chemical reactivity.     

Construction of isostructural hydrogen-bonded organic frameworks: limitations and possibilities of pore expansion

The library of isostructural porous frameworks enables a systematic survey to optimize the structure and functionality of porous materials. In contrary to metal–organic frameworks (MOFs) and covalent organic frameworks (COFs), a handful of isostructural frameworks have been reported for hydrogen-bonded organic frameworks (HOFs) due to the weakness of the bonds. Herein, we provide a rule-of-thumb to develop isostructural HOFs, where we demonstrate the construction of the third and fourth generation of isostructural HAT-based HOFs (TolHAT-1 and ThiaHAT-1) by considering three important structural factors, that are (1) directional H-bonding, (2) shape-fitted docking of the HAT core, and (3) modulation of peripheral moieties. Their structural and photo-physical properties including HCl vapor detection are presented. Moreover, TolHAT-1, ThiaHAT-1, and other isostructural HOFs (CPHAT-1 and CBPHAT-1) were thoroughly compared from the viewpoints of structures and properties. Importantly, molecular dynamics (MD) simulation proves to be rationally capable of evaluating the stability of isostructural HOFs. These results can accelerate the development of various isostructural molecular porous materials.

The library of isostructural porous frameworks enables a systematic survey to optimize the structure and functionality of porous materials.     

Monolayer nanosheets formed by liquid exfoliation of charge-assisted hydrogen-bonded frameworks

Hydrogen-bonded organic frameworks (HOFs) are a diverse and tunable class of materials, but their potential as free-standing two-dimensional nanomaterials has yet to be explored. Here we report the self-assembly of two layered hydrogen-bonded frameworks based on strong, charge-assisted hydrogen-bonding between carboxylate and amidinium groups. Ultrasound-assisted liquid exfoliation of both materials readily produces monolayer hydrogen-bonded organic nanosheets (HONs) with micron-sized lateral dimensions. The HONs show remarkable stability and maintain their extended crystallinity and monolayer structures even after being suspended in water at 80 °C for three days. These systems also exhibit efficient fluorescence quenching of an organic dye in organic solvents, superior to the quenching ability of the bulk frameworks. We anticipate that this approach will provide a route towards a diverse new family of molecular two-dimensional materials.

We report the liquid-phase ultrasonic exfoliation of two layered hydrogen-bonded frameworks into monolayer, micron-sized, and water-stable nanosheets (HONs) connected purely by hydrogen-bonding interactions.     

Controlling the alignment of 1D nanochannel arrays in oriented metal–organic framework films for host–guest materials design

Controlling the direction of molecular-scale pores enables the accommodation of guest molecular-scale species with alignment in the desired direction, allowing for the development of high-performance mechanical, thermal, electronic, photonic and biomedical organic devices (host–guest approach). Regularly ordered 1D nanochannels of metal–organic frameworks (MOFs) have been demonstrated as superior hosts for aligning functional molecules and polymers. However, controlling the orientation of MOF films with 1D nanochannels at commercially relevant scales remains a significant challenge. Here, we report the fabrication of macroscopically oriented films of Cu-based pillar-layered MOFs having regularly ordered 1D nanochannels. The direction of 1D nanochannels is controllable by optimizing the crystal growth process; 1D nanochannels align either perpendicular or parallel to substrates, offering molecular-scale pore arrays for a macroscopic alignment of functional guest molecules in the desired direction. Due to the fundamental interest and widespread technological importance of controlling the alignment of functional molecules and polymers in a particular direction, orientation-controllable MOF films will open up the possibility of realising the potential of MOFs in advanced technologies.

Orientation-controlled Cu₂(Linker)₂DABCO MOF films on macroscopic scales are fabricated for the development of high-performance devices; the direction of 1D nanochannels is controllable either perpendicular or parallel to substrates.     

Linking metal–organic cages pairwise as a design approach for assembling multivariate crystalline materials

Using metal–organic cages (MOCs) as preformed supermolecular building-blocks (SBBs) is a powerful strategy to design functional metal–organic frameworks (MOFs) with control over the pore architecture and connectivity. However, introducing chemical complexity into the network via this route is limited as most methodologies focus on only one type of MOC as the building-block. Herein we present the pairwise linking of MOCs as a design approach to introduce defined chemical complexity into porous materials. Our methodology exploits preferential Rh-aniline coordination and stoichiometric control to rationally link Cu₄L₄ and Rh₄L₄ MOCs into chemically complex, yet extremely well-defined crystalline solids. This strategy is expected to open up significant new possibilities to design bespoke multi-functional materials with atomistic control over the location and ordering of chemical functionalities.

A new strategy to design atomically precise multivariate metal–organic frameworks is presented. This is achieved by linking two preformed metal–organic cages via a precisely tuned Rh–aniline interaction.     

Linker depletion for missing cluster defects in non-UiO metal–organic frameworks

Defect engineering is a valuable tool to tune the properties of metal–organic frameworks. However, defect chemistry remains still predominantly limited to UiO-type MOFs. We describe the preferential formation of missing cluster defects in heterometallic titanium–organic frameworks of the MUV-10 family when synthesised in sub-stoichiometric linker conditions. Our results show the value of integrating experimental work, computational modelling and thorough characterization in rationalizing the impact of defects over the porosity and structure of this family of materials. Correlation of experiment with computational models reveals the dominance of missing cluster vacancies in the pore size distribution of defective MUV-10. These same models were used to investigate the correlation of defects by synchrotron X-ray diffraction. The diffraction at low reflection angles is dominated by diffuse scattering that is indicative of short-range order and cannot be indexed to the defective structural models generated. In addition to the low atomic scattering factor of titanium, these results confirm the need for high-resolution electron microscopy methods for modelling nanoscale disorder in titanium MOFs.

Synthesis of MUV-10 in sub-stoichiometric linker conditions favours the formation of missing cluster vacancies for direct impact in their porosity.     

A window-space-directed assembly strategy for the construction of supertetrahedron-based zeolitic mesoporous metal–organic frameworks with ultramicroporous apertures for selective gas adsorption

Despite their scarcity due to synthetic challenges, supertetrahedron-based metal–organic frameworks (MOFs) possess intriguing architectures, diverse functionalities, and superb properties that make them in-demand materials. Employing a new window-space-directed assembly strategy, a family of mesoporous zeolitic MOFs have been constructed herein from corner-shared supertetrahedra based on homometallic or heterometallic trimers [M₃(OH/O)(COO)₆] (M₃ = Co₃, Ni₃ or Co₂Ti). These MOFs consisted of close-packed truncated octahedral cages possessing a sodalite topology and large β-cavity mesoporous cages (∼22 Å diameter) connected by ultramicroporous apertures (∼5.6 Å diameter). Notably, the supertetrahedron-based sodalite topology MOF combined with the Co₂Ti trimer exhibited high thermal and chemical stability as well as the ability to efficiently separate acetylene (C₂H₂) from carbon dioxide (CO₂).

A series of supertetrahedron (ST)-based sodalite (sod)-topology zeolitic MOFs specimens ST-sod-MOFs featuring ultramicroporous square windows and a mesoporous sodcage have been synthesized via a window-space-directed assembly approach.     

Carbonization of single polyacrylonitrile chains in coordination nanospaces

It has been over half a century since polyacrylonitrile (PAN)-based carbon fibers were first developed. However, the mechanism of the carbonization reaction remains largely unknown. Structural evolution of PAN during the preoxidation reaction, a stabilization reaction, is one of the most complicated stages because many chemical reactions, including cyclization, dehydration, and cross-linking reactions, simultaneously take place. Here, we report the stabilization reaction of single PAN chains within the one-dimensional nanochannels of metal–organic frameworks (MOFs) to study an effect of interchain interactions on the stabilization process as well as the structure of the resulting ladder polymer (LP). The stabilization reaction of PAN within the MOFs could suppress the rapid generation of heat that initiates the self-catalyzed reaction and inevitably provokes many side-reactions and scission of PAN chains in the bulk state. Consequently, LP prepared within the MOFs had a more extended conjugated backbone than the bulk condition.

Accommodation of polyacrylonitrile in MOFs facilitated and regulated the transformation to ladder polymer in the carbonization process.     

Tetrathiafulvalene-based covalent organic frameworks for ultrahigh iodine capture

To safeguard the development of nuclear energy, practical techniques for capture and storage of radioiodine are of critical importance but remain a significant challenge. Here we report the synergistic effect of physical and chemical adsorption of iodine in tetrathiafulvalene-based covalent organic frameworks (COFs), which can markedly improve both iodine adsorption capacity and adsorption kinetics due to their strong interaction. These functionalized architectures are designed to have high specific surface areas (up to 2359 m² g⁻¹) for efficient physisorption of iodine, and abundant tetrathiafulvalene functional groups for strong chemisorption of iodine. We demonstrate that these frameworks achieve excellent iodine adsorption capacity (up to 8.19 g g⁻¹), which is much higher than those of other materials reported so far, including silver-doped adsorbents, inorganic porous materials, metal–organic frameworks, porous organic frameworks, and other COFs. Furthermore, a combined theoretical and experimental study, including DFT calculations, electron paramagnetic resonance spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy, reveals the strong chemical interaction between iodine and the frameworks of the materials. Our study thus opens an avenue to construct functional COFs for a critical environment-related application.

The synergistic effect of physical and chemical adsorption of iodine in tetrathiafulvalene-based covalent organic frameworks (COFs) has been explored. The iodine adsorption capacity of these materials is higher than other materials reported so far.     

Rational incorporation of defects within metal–organic frameworks generates highly active electrocatalytic sites

The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control. An emerging strategy to generate coordinatively-unsaturated active sites is through the use of organic linkers that lack a functional group that would usually bind with the metal nodes. To execute this strategy, we synthesize a model MOF, Ni-MOF-74 and incorporate a fraction of 2-hydroxyterephthalic acid in place of 2,5-dihydroxyterephthalic acid. The defective MOF, Ni-MOF-74D, is evaluated vs. the nominally defect-free Ni-MOF-74 with a host of ex situ and in situ spectroscopic and electroanalytical techniques, using the oxidation of hydroxymethylfurtural (HMF) as a model reaction. The data indicates that Ni-MOF-74D features a set of 4-coordinate Ni–O₄ sites that exhibit unique vibrational signatures, redox potentials, binding motifs to HMF, and consequently superior electrocatalytic activity relative to the original Ni-MOF-74 MOF, being able to convert HMF to the desired 2,5-furandicarboxylic acid at 95% yield and 80% faradaic efficiency. Furthermore, having such rationally well-defined catalytic sites coupled with in situ Raman and infrared spectroelectrochemical measurements enabled the deduction of the reaction mechanism in which co-adsorbed *OH functions as a proton acceptor in the alcohol oxidation step and carries implications for catalyst design for heterogeneous electrosynthetic reactions en route to the electrification of the chemical industry.

The allure of metal–organic frameworks (MOFs) in heterogeneous electrocatalysis is that catalytically active sites may be designed a priori with an unparalleled degree of control.     

Infrared crystallography for framework and linker orientation in metal–organic framework films

Pore alignment and linker orientation influence diffusion and guest molecule interactions in metal–organic frameworks (MOFs) and play a pivotal role for successful utilization of MOFs. The crystallographic orientation and the degree of orientation of MOF films are generally determined using X-ray diffraction. However, diffraction methods reach their limit when it comes to very thin films, identification of chemical connectivity or the orientation of organic functional groups in MOFs. Cu-based 2D MOF and 3D MOF films prepared via layer-by-layer method and from aligned Cu(OH)₂ substrates were studied with polarization-dependent Fourier-transform infrared (FTIR) spectroscopy in transmission and attenuated total reflection configuration. Thereby, the degrees for in-plane and out-of-plane orientation, the aromatic linker orientation and the initial alignment during layer-by-layer MOF growth, which is impossible to investigate by laboratory XRD equipment, was determined. Experimental IR spectra correlate with theoretical explanations, paving the way to expand the principle of IR crystallography to oriented, organic–inorganic hybrid films beyond MOFs.

Polarization-dependent infrared spectroscopy of oriented metal organic framework films fills the information gap left by diffraction methods and gives access to the orientation of the aromatic linker and initial orientation of ultra-thin films.     

2D framework materials for energy applications

In recent years a massive increase in publications on conventional 2D materials (graphene, h-BN, MoS₂) is documented, accompanied by the transfer of the 2D concept to porous (crystalline) materials, such as ordered 2D layered polymers, covalent-organic frameworks, and metal–organic frameworks. Over the years, the 3D frameworks have gained a lot of attention for use in applications, ranging from electronic devices to catalysis, and from information to separation technologies, mostly due to the modular construction concept and exceptionally high porosity. A key challenge lies in the implementation of these materials into devices arising from the deliberate manipulation of properties upon delamination of their layered counterparts, including an increase in surface area, higher diffusivity, better access to surface sites and a change in the band structure. Within this minireview, we would like to highlight recent achievements in the synthesis of 2D framework materials and their advantages for certain applications, and give some future perspectives.

In recent years the 2D concept has been transferred from conventional 2D materials to porous 2D framework materials. This minireview takes a closer look onto the preparation of 2D framework materials and their merits for energy applications.     

Interplay of structural dynamics and electronic effects in an engineered assembly of pentacene in a metal–organic framework

Charge carrier mobility is an important figure of merit to evaluate organic semiconductor (OSC) materials. In aggregated OSCs, this quantity is determined by inter-chromophoric electronic and vibrational coupling. These key parameters sensitively depend on structural properties, including the density of defects. We have employed a new type of crystalline assembly strategy to engineer the arrangement of the OSC pentacene in a structure not realized as crystals to date. Our approach is based on metal–organic frameworks (MOFs), in which suitably substituted pentacenes act as ditopic linkers and assemble into highly ordered π-stacks with long-range order. Layer-by-layer fabrication of the MOF yields arrays of electronically coupled pentacene chains, running parallel to the substrate surface. Detailed photophysical studies reveal strong, anisotropic inter-pentacene electronic coupling, leading to efficient charge delocalization. Despite a high degree of structural order and pronounced dispersion of the 1D-bands for the static arrangement, our experimental results demonstrate hopping-like charge transport with an activation energy of 64 meV dominating the band transport over a wide range of temperatures. A thorough combined quantum mechanical and molecular dynamics investigation identifies frustrated localized rotations of the pentacene cores as the reason for the breakdown of band transport and paves the way for a crystal engineering strategy of molecular OSCs that independently varies the arrangement of the molecular cores and their vibrational degrees of freedom.

Pentacene assembled into 1D arrays using a metal–organic framework (MOF) approach. This cofacial packing motif, which is not present in pentacene bulk, shows an interesting interplay of band-like and hopping-type transport.     

Single-step synthesis and interface tuning of core–shell metal–organic framework nanoparticles

Control over the spatial distribution of components in metal–organic frameworks has potential to unlock improved performance and new behaviour in separations, sensing and catalysis. We report an unprecedented single-step synthesis of multi-component metal–organic framework (MOF) nanoparticles based on the canonical ZIF-8 (Zn) system and its Cd analogue, which form with a core–shell structure whose internal interface can be systematically tuned. We use scanning transmission electron microscopy, X-ray energy dispersive spectroscopy and a new composition gradient model to fit high-resolution X-ray diffraction data to show how core–shell composition and interface characteristics are intricately controlled by synthesis temperature and reaction composition. Particle formation is investigated by in situ X-ray diffraction, which reveals that the spatial distribution of components evolves with time and is determined by the interplay of phase stability, crystallisation kinetics and diffusion. This work opens up new possibilities for the control and characterisation of functionality, component distribution and interfaces in MOF-based materials.

Core–shell metal–organic framework nanoparticles have been synthesised in which the internal interface and distribution of components is found to be highly tunable using simple variations in reaction conditions.