Leveraging metal node-linker self-assembly to access functional anisotropy of zirconium-based MOF-on-MOF epitaxial heterostructure thin films.

Chemically robust, functional porous materials are imperative for designing novel membranes for chemical separation and heterogeneous catalysts. Among the array of potential materials, zirconium (Zr)-based metal-organic frameworks (MOFs) have garnered considerable attention, and have been investigated for applications related to gas separation and storage, and catalysis. However, a significant challenge with Zr-MOFs lies in their processibility, particularly in achieving homogenous thin films and controlling functional anisotropy. The recent developments in MOF thin film fabrication methodologies do not yield a solution to achieve mild reaction condition growth of Zr-MOF thin films with epitaxial MOF-on-MOF geometry (i.e. functional anisotropy). In the current work, we have devised a straightforward methodology under room temperature conditions, which enables epitaxial, oriented MOF-on-MOF thin film growth. This achievement is accomplished through a stepwise self-assembly approach involving Zr nodes and linkers on a functionalized substrate. This de novo developed strategy of functionality design is demonstrated for UiO-66 (University of Oslo) type Zr-MOFs. We have demonstrated the precise placement of chemical functionalities within the thin film structure, allowing for controlled chemical diffusion and regulation of diffusion selectivity.

Noncovalent interaction guided selectivity of haloaromatic isomers in a flexible porous coordination polymer.

Porous, supramolecular structures exhibit preferential encapsulation of guest molecules, primarily by means of differences in the order of (noncovalent) interactions. The encapsulation preferences can be for geometry (dimension and shape) and the chemical nature of the guest. While geometry-based sorting is relatively straightforward using advanced porous materials, designing a "chemical nature" specific host is not. To introduce "chemical specificity", the host must retain an accessible and complementary recognition site. In the case of a supramolecular, porous coordination polymer (PCP) [Zn(o-phen)(ndc)] (o-phen: 1,10-phenanthroline, ndc: 2,6-naphthalenedicarboxylate) host, equipped with an adaptable recognition pocket, we have discovered that the preferential encapsulation of a haloaromatic isomer is not only for dimension and shape, but also for the "chemical nature" of the guest. This selectivity, i.e., preference for the dimension, shape and chemical nature, is not guided by any complementary recognition site, which is commonly required for "chemical specificity". Insights from crystal structures and computational studies unveil that the differences in the different types of noncovalent host-guest interaction strengths, acting in a concerted fashion, yield the unique selectivity.

A roadmap to enhance gas permselectivity in metal-organic framework-based mixed-matrix membranes.

Performing gas separation at high efficiency with minimum energy input and reduced carbon footprint is a major challenge. While several separation methods exist at various technology readiness levels, porous membrane-based separation is considered as a disruptive technology. To attain sustainability and required efficiency, different approaches of membrane design have been explored. However, the selectivity-permeation trade-off and membrane aging have restricted further advancement. In this regard, a new generation composite made of organic polymers and metal-organic framework (MOF) fillers shows substantial promise. Organic polymer matrix allows easy processibility, but it has poor permselectivity for gas molecules. Metal-organic frameworks are excellent sieving materials; however, they suffer from poor processibility issues. A combination of these two components makes an ideal sieving membrane, which can potentially outnumber the existing energy intensive distillation strategies. In this perspective, we have discussed key indices that regulate gas permselectivity by a careful selection of the existing literature. While the target gas flux and selectivity values have been a part of many previous reviews and articles, we have presented a concise discussion on the interface design of the MOF-polymer membrane, morphology, and orientation control of MOF fillers in the matrix. Following this, a future roadmap to overcome challenges related to MOF-polymer interfacial defects is outlined.

Tunable J-type aggregation of silicon phthalocyanines in a surface-anchored metal-organic framework thin film.

Organic chromophores and semiconductors, like anthracene, pentacene, perylene, and porphyrin, are prone to aggregation, and their packing in the solid state is often hard to predict and difficult to control. As the condensed phase structures of these chromophores and semiconductors are of crucial importance for their optoelectronic functionality, strategies to control their assembly and provide new structural motifs are important. One such approach uses metal-organic frameworks (MOFs); the organic chromophore is converted into a linker and connected by metal ions or nodes. The spatial arrangement of the organic linkers can be well-defined in a MOF, and hence optoelectronic functions can be adjusted accordingly. We have used such a strategy to assemble a phthalocyanine chromophore and illustrated that the electronic inter-phthalocyanine coupling can be rationally tuned by introducing bulky side grounds to increase steric hindrance. We have designed new phthalocyanine linkers and using a layer-by-layer liquid-phase epitaxy strategy thin films of phthalocyanine-based MOFs have been fabricated and their photophysical properties explored. It was found that increasing the steric hindrance around the phthalocyanine reduced the effect of J-aggregation in the thin film structures.

Chemically routed interpore molecular diffusion in metal-organic framework thin films.

Transport diffusivity of molecules in a porous solid is constricted by the rate at which molecules move from one pore to the other, along the concentration gradient, i.e. by following Fickian diffusion. In heterogeneous porous materials, i.e. in the presence of pores of different sizes and chemical environments, diffusion rate and directionality remain tricky to estimate and adjust. In such a porous system, we have realized that molecular diffusion direction can be orthogonal to the concentration gradient. To experimentally determine this complex diffusion rate dependency and get insight of the microscopic diffusion pathway, we have designed a model nanoporous structure, metal-organic framework (MOF). In this model two chemically and geometrically distinct pore windows are spatially oriented by an epitaxial, layer-by-layer growth method. The specific design of the nanoporous channels and quantitative mass uptake rate measurements have indicated that the mass uptake is governed by the interpore diffusion along the direction orthogonal to the concentration gradient. This revelation allows chemically carving the nanopores, and accelerating the interpore diffusion and kinetic diffusion selectivity.

Stacking Lanthanide-MOF Thin Films to Yield Highly Sensitive Optical Thermometers.

Easy-to-integrate, remote read-out thermometers with fast response are of huge interest in numerous application fields. In the context of optical read-out devices, sensors based on the emission of lanthanides (Eu(III), Tb(III)) are particularly promising. Here, by using a layer-by-layer (LbL) approach in the liquid-phase epitaxy process, a series of continuous, low-thickness lanthanide-MIL-103 SURMOFs were fabricated to yield highly sensitive thermometers with optical readout. These Ln-SURMOFs exhibit remarkable temperature-sensing photoluminescence behavior, which can be read out using the naked eye. High transmittance is realized as well by precisely controlling the film thickness and the quality of these Ln-SURMOF thermometers. Moreover, we demonstrate that the thermal sensitivity can be improved in the temperature regime above 120 K, by controlling the energy transfer between Tb(III) and Eu(III). This performance is achieved by employing a sophisticated supramolecular architecture, namely MOF-on-MOF heteroepitaxy.

Charge transfer in metal-organic frameworks.

Metal-organic frameworks (MOFs, also known as porous coordination polymers or PCPs) are a novel class of crystalline porous material. The tailorable porous structure, in terms of size, geometry and function, has attracted the attention of researchers across all disciplines of materials science. One of the many exciting aspects of MOFs is that through directional and reversible coordination bonding, organic linkers (chromophores with metal-coordinating functional groups) and metal ions (and clusters) can be spatially organized in a preconceived geometry. The well-defined spatial geometry of the metals and linkers is very advantageous for optoelectronic functions (solar cells, light-emitting diodes, photocatalysts) of the materials. This feature article evaluates the scope of charge transfer (CT) interactions in MOFs, involving the organic linkers and metal ion or cluster components. Irrespective of the type (size, shape, electronic property) of organic chromophores involved, MOFs provide an insightful path to design and make the CT process efficient. The selected examples of MOFs with CT characteristics do not only illustrate the design principles but render a pathway towards understanding the complex photophysical processes and implementing those for future optoelectronic and catalytic applications.

Photoinduced Delamination of Metal-Organic Framework Thin Films by Spatioselective Generation of Reactive Oxygen Species.

Metal-organic frameworks (MOFs) built from different building units offer functionalities going far beyond gas storage and separation. In connection with advanced applications, e.g., in optoelectronics, hierarchical MOF-on-MOF structures fabricated using sophisticated methodologies have recently become particularly attractive. Here, we demonstrate that the structural complexity of MOF-based architectures can be further increased by employing highly spatioselective photochemistry. Using a layer-by-layer, quasi-epitaxial synthesis method, we realized a photoactive MOF-on-MOF hetero-bilayer consisting of a porphyrinic bottom layer and a tetraphenylethylene (TPE)-based top layer. Illumination of the monolithic thin film with visible light in the presence of oxygen gas results in the generation of reactive oxygen species (1O2) in the porphyrinic bottom layer, which lead to a photocleavage of the TPE units at the internal interface. We demonstrate that this spatioselective photochemistry can be utilized to delaminate the top layers, yielding two-dimensional (2D) MOF sheets with well-defined thickness. Experiments using atomic force microscopy (AFM) demonstrate that these platelets can be transferred onto other substrates, thus opening up the possibility of fabricating planar MOF structures using photolithography.

Multicolour lanthanide(III) porous 1D coordination polymers: tunable wide spectrum emission and efficient CuII sensing.

Five isostructural 1D porous coordination polymers (PCPs) with a general formula of {[M(L)(DMF)(H2O)]·1.5H2O}n [M = TbIII (1), EuIII (2), YbIII (3), NdIII (4) and ErIII (5)] have been synthesized using a flexible tripodal organic linker (L) and characterized. TbIII (1) and EuIII (2) PCPs exhibit metal-based green and red emission, respectively, whereas YbIII (3), NdIII (4) and ErIII (5) PCPs show near-infrared (NIR) emission. Doping EuIII in 1 in a precisely controlled stoichiometric amount leads to different mixed lanthanide PCPs, {[Tb1-xEux(L)(DMF)(H2O)]·1.5H2O}n (1a-1f) that show tunable emission including that of bright white light. The PCPs decorated with Lewis basic -O- binding sites make them potential candidates for the binding and selective sensing of traces of CuII ions, and this is illustrated for PCP 2 (limit of detection = 0.69 ± 0.02 ppm). The photoluminescence of 2 can be recovered by the introduction of a chelating ligand ethylenediaminetetraacetic acid (EDTA) without any structural disintegration, indicating the potential of the lanthanide PCPs for future sensing applications.

Avoiding the Center-Symmetry Trap: Programmed Assembly of Dipolar Precursors into Porous, Crystalline Molecular Thin Films.

Liquid-phase, quasi-epitaxial growth is used to stack asymmetric, dipolar organic compounds on inorganic substrates, permitting porous, crystalline molecular materials that lack inversion symmetry. This allows material fabrication with built-in electric fields. A new programmed assembly strategy based on metal-organic frameworks (MOFs) is described that facilitates crystalline, noncentrosymmetric space groups for achiral compounds. Electric fields are integrated into crystalline, porous thin films with an orientation normal to the substrate. Changes in electrostatic potential are detected via core-level shifts of marker atoms on the MOF thin films and agree with theoretical results. The integration of built-in electric fields into organic, crystalline, and porous materials creates possibilities for band structure engineering to control the alignment of electronic levels in organic molecules. Built-in electric fields may also be used to tune the transfer of charges from donors loaded via programmed assembly into MOF pores. Applications include organic electronics, photonics, and nonlinear optics, since the absence of inversion symmetry results in a clear second-harmonic generation signal.

A Dynamic Chemical Clip in Supramolecular Framework for Sorting Alkylaromatic Isomers using Thermodynamic and Kinetic Preferences.

Adsorptive chemical separation is at the forefront of future technologies, for use in chemical and petrochemical industries. In this process, a porous adsorbent selectively allows a single component from a mixture of three or more chemical components to be adsorbed or permeate. To separate the unsorted chemicals, a different adsorbent is needed. A unique adsorbent which can recognize and separate each of the chemicals from a mixture of three or more components is the necessity for the next generation porous materials. In this regard, we demonstrate a "dynamic chemical clip" in a supramolecular framework capable of thermodynamic and kinetics-based chemical separation. The dynamic space, featuring a strong preference for aromatic guests through π-π and C-H⋅⋅⋅π interactions and adaptability, can recognize the individual chemical isomers from mixtures and separate those based on thermodynamic and kinetic factors. The liquid-phase selectivity and separation of the aromatic isomers are possible by the adaptability of the "chemical clip" and here we elucidate the prime factors in a combinatorial approach involving crystallographic evidence and detailed computational studies.

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.

Modular Synthesis of trans-A2 B2 -Porphyrins with Terminal Esters: Systematically Extending the Scope of Linear Linkers for Porphyrin-Based MOFs.

Differently functionalized porphyrin linkers represent the key compounds for the syntheses of new porphyrin-based metal-organic frameworks (MOFs), which have gathered great interest within the last two decades. Herein we report the synthesis of a large range of 5,15-bis(4-ethoxycarbonylphenyl)porphyrin derivatives, through Suzuki and Sonogashira cross-coupling reactions of an easily accessible corresponding meso-dibrominated trans-A2 B2 -porphyrin with commercially available boronic acids or terminal alkynes. The resulting porphyrins were fully characterized through NMR, MS, and IR spectroscopy and systematically investigated through UV/Vis absorption. Finally, selected structures were saponified to the corresponding carboxylic acids and subsequently proven to be suitable for the synthesis of surface-anchored MOF thin films.

Introducing electrical conductivity to metal-organic framework thin films by templated polymerization of methyl propiolate.

We herein present a case study on the templated, Pd-catalyzed polymerization reaction of methyl propiolate in the confined pore space of three different surface anchored metal-organic framework (SURMOF) systems in order to introduce electrical conductivity to MOF thin films and provide predictions for potential device integrations. To gain comprehensive insight into the influence of the template on polymerization, we chose Cu(bpdc), Cu2(bdc)2(dabco) and HKUST-1 because of their different types of pore channels, 1D, quasi-1D and 3D, and their free pore volumes. Well-defined MOF thin films were prepared using layer-by-layer deposition, which allows for the application of several characterization techniques not applicable for conventional powder MOFs. With SEM, AFM, XRD, MALDI-ToF/MS, ToF-SIMS and QCM, we were able to investigate the behaviour of the polymer formation. For lower dimensional pore channels, we find a depot-like release of monomeric units leading to top-layer formation determined by desorption kinetics, whereas for the 3D channels, quick release of an excess amount of monomers was observed and polymerization proceeds perfectly. Despite polymerization issues, control over the maximum chain lengths and the molecular weight distribution was achieved depending on the dimensionality of the pore systems. For the HKUST-1 system, polymerization was optimized and we were able to measure the electrical conductivity introduced by the conjugated polymer inside the channels.

Crystalline assembly of perylene in metal-organic framework thin film: J-aggregate or excimer? Insight into the electronic structure.

The spatial orientation of chromophores defines the photophysical and optoelectronic properties of a material and serves as the main tunable parameter for tailoring functionality. Controlled assembly for achieving a predefined spatial orientation of chromophores is rather challenging. Metal-organic frameworks (MOFs) are an attractive platform for exploring the virtually unlimited chemical space of organic components and their self-assembly for device optimization. Here, we demonstrate the impact of interchromophore interactions on the photophysical properties of a surface-anchored MOF (SURMOF) based on 3,9-perylenedicarboxylicacid linkers. We predict the structural assembly of the perylene molecules in the MOF via robust periodic density functional theory calculations and discuss the impact of unit topology and π-π interaction patterns on spectroscopic and semiconducting properties of the MOF films. We explain the dual nature of excited states in the perylene MOF, where strong temperature-modulated excimer emission, enhanced by the formation of perylene J-aggregates, and low stable monomer emission are observed. We use band-like and hopping transport mechanisms to predict semiconducting properties of perylene SURMOF-2 films as a function of inter-linker interactions, demonstrating both p-type and n-type conduction mechanisms. Hole carrier mobility up to 7.34 cm2Vs-1is predicted for the perylene SURMOF-2. The results show a promising pathway towards controlling excimer photophysics in a MOF while controlling charge carrier mobility on the basis of a predictive model.

Exciton Coupling and Conformational Changes Impacting the Excited State Properties of Metal Organic Frameworks.

In recent years, the photophysical properties of crystalline metal-organic frameworks (MOFs) have become increasingly relevant for their potential application in light-emitting devices, photovoltaics, nonlinear optics and sensing. The availability of high-quality experimental data for such systems makes them ideally suited for a validation of quantum mechanical simulations, aiming at an in-depth atomistic understanding of photophysical phenomena. Here we present a computational DFT study of the absorption and emission characteristics of a Zn-based surface-anchored metal-organic framework (Zn-SURMOF-2) containing anthracenedibenzoic acid (ADB) as linker. Combining band-structure and cluster-based simulations on ADB chromophores in various conformations and aggregation states, we are able to provide a detailed explanation of the experimentally observed photophysical properties of Zn-ADB SURMOF-2: The unexpected (weak) red-shift of the absorption maxima upon incorporating ADB chromophores into SURMOF-2 can be explained by a combination of excitonic coupling effects with conformational changes of the chromophores already in their ground state. As far as the unusually large red-shift of the emission of Zn-ADB SURMOF-2 is concerned, based on our simulations, we attribute it to a modification of the exciton coupling compared to conventional H-aggregates, which results from a relative slip of the centers of neighboring chromophores upon incorporation in Zn-ADB SURMOF-2.

Tuning Optical Properties by Controlled Aggregation: Electroluminescence Assisted by Thermally-Activated Delayed Fluorescence from Thin Films of Crystalline Chromophores.

Several photophysical properties of chromophores depend crucially on intermolecular interactions. Thermally-activated delayed fluorescence (TADF) is often influenced by close packing of the chromophore assembly. In this context, the metal-organic framework (MOF) approach has several advantages: it can be used to steer aggregation such that the orientation within aggregated structures can be predicted using rational approaches. We demonstrate this design concept for a DPA-TPE (diphenylamine-tetraphenylethylene) chromophore, which is non-emissive in its solvated state due to vibrational quenching. Turning this DPA-TPE into a ditopic linker makes it possible to grow oriented MOF thin films exhibiting pronounced green electroluminescence with low onset voltages. Measurements at different temperatures clearly demonstrate the presence of TADF. Finally, this work reports that the layer-by-layer process used for MOF thin film deposition allows the integration of the TADF-DPA-TPE in a functioning LED device.

Guest-Responsive Reversible Electron Transfer in a Crystalline Porous Framework Supported by a Dynamic Building Node.

We demonstrate a redox-active, crystalline donor-acceptor (D-A) assembly in which the electron transfer (ET) process can be reversibly switched. This ET process, induced by a guest-responsive structural transformation at room temperature, is realized in a porous, metal-organic framework (MOF), having anthracene (D)-naphthalenediimide (A) as struts. A control MOF structure obtained by a solvent-assisted linker exchange (SALE) method, replacing an acceptor strut with a neutral one, supported the switchable electronic states in the D-A MOF. Combined investigations with X-ray diffraction, spectroscopy, and theoretical analyses revealed the dynamic metal paddle-wheel node as a critical unit for controlling structural flexibility and the corresponding unprecedented ET process.

Guest-responsive polaritons in a porous framework: chromophoric sponges in optical QED cavities.

Introducing porous material into optical cavities is a critical step toward the utilization of quantum-electrodynamical (QED) effects for advanced technologies, e.g. in the context of sensing. We demonstrate that crystalline, porous metal-organic frameworks (MOFs) are well suited for the fabrication of optical cavities. In going beyond functionalities offered by other materials, they allow for the reversible loading and release of guest species into and out of optical resonators. For an all-metal mirror-based Fabry-Perot cavity we yield strong coupling (∼21% Rabi splitting). This value is remarkably large, considering that the high porosity of the framework reduces the density of optically active moieties relative to the corresponding bulk structure by ∼60%. Such a strong response of a porous chromophoric scaffold could only be realized by employing silicon-phthalocyanine (SiPc) dyes designed to undergo strong J-aggregation when assembled into a MOF. Integration of the SiPc MOF as active component into the optical microcavity was realized by employing a layer-by-layer method. The new functionality opens up the possibility to reversibly and continuously tune QED devices and to use them as optical sensors.

Correction: Guest-responsive polaritons in a porous framework: chromophoric sponges in optical QED cavities.

[This corrects the article DOI: 10.1039/D0SC02436H.].