Harvesting Water from Air with High-Capacity, Stable Furan-Based Metal-Organic Frameworks.

We synthesized two isoreticular furan-based metal-organic frameworks (MOFs), MOF-LA2-1(furan) and MOF-LA2-2(furan) with rod-like secondary building units (SBUs) featuring 1D channels, as sorbents for atmospheric water harvesting (LA = long arm). These aluminum-based MOFs demonstrated a combination of high water uptake and stability, exhibiting working capacities of 0.41 and 0.48 gwater/gMOF (under isobaric conditions of 1.70 kPa), respectively. Remarkably, both MOFs showed a negligible loss in water uptake after 165 adsorption-desorption cycles. These working capacities rival that of MOF-LA2-1(pyrazole), which has a working capacity of 0.55 gwater/gMOF. The current MOFs stand out for their high water stability, as evidenced by 165 cycles of water uptake and release. MOF-LA2-2(furan) is the first aluminum MOF to employ a double 'long arm' extension strategy, which is confirmed through single-crystal X-ray diffraction (SCXRD). The MOFs were synthesized by using a straightforward synthesis route. This study offers valuable insights into the design of durable, water-stable MOFs and underscores their potential for efficient water harvesting.

Shaping the Water-Harvesting Behavior of Metal-Organic Frameworks Aided by Fine-Tuned GPT Models.

We construct a data set of metal-organic framework (MOF) linkers and employ a fine-tuned GPT assistant to propose MOF linker designs by mutating and modifying the existing linker structures. This strategy allows the GPT model to learn the intricate language of chemistry in molecular representations, thereby achieving an enhanced accuracy in generating linker structures compared with its base models. Aiming to highlight the significance of linker design strategies in advancing the discovery of water-harvesting MOFs, we conducted a systematic MOF variant expansion upon state-of-the-art MOF-303 utilizing a multidimensional approach that integrates linker extension with multivariate tuning strategies. We synthesized a series of isoreticular aluminum MOFs, termed Long-Arm MOFs (LAMOF-1 to LAMOF-10), featuring linkers that bear various combinations of heteroatoms in their five-membered ring moiety, replacing pyrazole with either thiophene, furan, or thiazole rings or a combination of two. Beyond their consistent and robust architecture, as demonstrated by permanent porosity and thermal stability, the LAMOF series offers a generalizable synthesis strategy. Importantly, these 10 LAMOFs establish new benchmarks for water uptake (up to 0.64 g g-1) and operational humidity ranges (between 13 and 53%), thereby expanding the diversity of water-harvesting MOFs.

Structural Chemistry of Zeolitic Imidazolate Frameworks.

Zeolitic imidazolate frameworks (ZIFs) are a subclass of reticular structures based on tetrahedral four-connected networks of zeolites and minerals. They are composed of transition-metal ions and imidazolate-type linkers, and their pore size and shape, surface area, and functionality can be precisely controlled. Despite their potential, two questions remain unanswered: how to synthesize more diverse ZIF structures and how ZIFs differentiate from other crystalline solids. In other words, how can we use our understanding of their unique structures to better design and synthesize ZIFs? In this Review, we first summarize the methods for synthesizing a wide range of ZIFs. We then review the crystal structure of ZIFs and describe the relationship between their structure and properties using an in-depth analysis. We also discuss several important and intrinsic features that make ZIFs stand out from MOFs and discrete molecular cages. Finally, we outline the future direction for this class of porous crystals.

Calcium l-Malate and d-Tartarate Frameworks as Adjuvants for the Sustainable Delivery of a Fungicide.

Agrichemical adjuvants that combine a highly selective, efficient, and active mode of operation are critically needed to realize a more sustainable approach to their usage. Herein, we report the synthesis and full characterization of two new metal-organic frameworks (MOFs), termed UPMOF-1 and UPMOF-2, that were constructed from eco-friendly Ca2+ ions and naturally occurring, low-molecular weight plant acids, l-malic and d-tartaric acid, respectively. Upon structural elucidation of both MOFs, a widely used fungicide, hexaconazole (Hex), was loaded on the structures, reaching binding affinities of -5.0 and -3.5 kcal mol-1 and loading capacities of 63% and 62% for Hex@UPMOF-1 and Hex@UPMOF-2, respectively, as a result of the formation of stable host-guest interactions. Given the framework chemistry of the MOFs and their predisposition to disassembly under relevant agricultural conditions, the sustained release kinetics were determined to show nearly quantitative release (98% and 95% for Hex@UPMOF-1 and Hex@UPMOF-2, respectively) after >500 h, a release profile drastically different than the control (>80% release in 24 h), from which the high efficiency of these new systems was established. To confirm their high selectivity and activity, in vitro and in vivo studies were performed to illustrate the abilities of Hex@UPMOF-1 and Hex@UPMOF-2 to combat the known aggressive pathogen Ganoderma boninense that causes basal stem rot disease in oil palm. Accordingly, at an extremely low concentration of 0.05 µg mL-1, both Hex@UPMOF-1 and Hex@UPMOF-2 were demonstrated to completely inhibit (100%) G. boninense growth, and during a 26 week in vivo nursery trial, the progression of basal stem rot infection was completely halted upon treatment with Hex@UPMOF-1 and Hex@UPMOF-2 and seedling growth was accelerated given the additional nutrients supplied via the disassembly of the MOFs. This study represents a significant step forward in the design of adjuvants to support the environmentally responsible use of agrichemical crop protection.

ChatGPT Research Group for Optimizing the Crystallinity of MOFs and COFs.

We leveraged the power of ChatGPT and Bayesian optimization in the development of a multi-AI-driven system, backed by seven large language model-based assistants and equipped with machine learning algorithms, that seamlessly orchestrates a multitude of research aspects in a chemistry laboratory (termed the ChatGPT Research Group). Our approach accelerated the discovery of optimal microwave synthesis conditions, enhancing the crystallinity of MOF-321, MOF-322, and COF-323 and achieving the desired porosity and water capacity. In this system, human researchers gained assistance from these diverse AI collaborators, each with a unique role within the laboratory environment, spanning strategy planning, literature search, coding, robotic operation, labware design, safety inspection, and data analysis. Such a comprehensive approach enables a single researcher working in concert with AI to achieve productivity levels analogous to those of an entire traditional scientific team. Furthermore, by reducing human biases in screening experimental conditions and deftly balancing the exploration and exploitation of synthesis parameters, our Bayesian search approach precisely zeroed in on optimal synthesis conditions from a pool of 6 million within a significantly shortened time scale. This work serves as a compelling proof of concept for an AI-driven revolution in the chemistry laboratory, painting a future where AI becomes an efficient collaborator, liberating us from routine tasks to focus on pushing the boundaries of innovation.

Cobalt Hydrogen-Bonded Organic Framework as a Visible Light-Driven Photocatalyst for CO2 Cycloaddition Reaction.

A novel cobalt hydrogen-bonded organic framework (Co-HOF, C24H14CoN4O8) was synthesized from a mixed linker, that is, 2,5-pyridinedicarboxylic acid (PDC) and 2,2'-bipyridyl (BPY) linkers and cobalt ion through a simple, one-pot, low-cost, and scalable solvothermal method. The Co-HOF was fully characterized using several analytical and spectroscopic techniques including single-crystal X-ray diffraction, diffuse reflectance spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray, and X-ray photoelectron spectroscopy. The Co-HOF exhibits high thermal and chemical stabilities compared to previously reported HOF materials. Moreover, Co-HOF shows excellent photocatalytic activity under visible light irradiation due to its narrow band gap of 2.05 eV. The cycloaddition reaction of CO2 to variable epoxides was investigated to evaluate the photocatalytic performance of Co-HOF under visible light radiation and was found to produce the corresponding cyclic carbonates in yields up to 99.9%.

Lanthanide(III) (Er/Ho) coordination polymers for a photocatalytic CO2 cycloaddition reaction.

Two new isostructural carboxylate-bridged lanthanide ribbons having the chemical formula [Ln2(4-ABA)6]n [4-ABA = 4-aminobenzoate, Ln: holmium (Ho) and erbium (Er)] were synthesized by a solvothermal method and fully characterized using multiple analytical, spectroscopic, and computational techniques. Single-crystal X-ray diffraction analysis reveals that both lanthanide coordination polymers (Ln-CPs) exhibit linear ribbon-like structures built up by dinuclear Ln2(4-ABA)6 units and bridged by carboxylate groups. Ln-CPs showed remarkably high thermal and chemical stabilities. Ho-CP and Er-CP exhibited similar band gaps of 3.21 eV and 3.22 eV, respectively, showing their photocatalytic ability under UV light. The photocatalytic activities of Ln-CPs were examined in the CO2 cycloaddition of epoxides to cyclic carbonates under solvent-free conditions, and full conversion (yields up to 99.9%) to the product was achieved. Ln-CP photocatalysts retained the same product yields over five consecutive cycles. Additionally, the experimental magnetic studies indicated that both Ln-CP crystals are antiferromagnetic at low T, which is confirmed by density functional theory calculations.

BioMOF-Based Anti-Cancer Drug Delivery Systems.

A variety of nanomaterials have been developed specifically for biomedical applications, such as drug delivery in cancer treatment. These materials involve both synthetic and natural nanoparticles and nanofibers of varying dimensions. The efficacy of a drug delivery system (DDS) depends on its biocompatibility, intrinsic high surface area, high interconnected porosity, and chemical functionality. Recent advances in metal-organic framework (MOF) nanostructures have led to the achievement of these desirable features. MOFs consist of metal ions and organic linkers that are assembled in different geometries and can be produced in 0, 1, 2, or 3 dimensions. The defining features of MOFs are their outstanding surface area, interconnected porosity, and variable chemical functionality, which enable an endless range of modalities for loading drugs into their hierarchical structures. MOFs, coupled with biocompatibility requisites, are now regarded as highly successful DDSs for the treatment of diverse diseases. This review aims to present the development and applications of DDSs based on chemically-functionalized MOF nanostructures in the context of cancer treatment. A concise overview of the structure, synthesis, and mode of action of MOF-DDS is provided.

Covalent Organic Frameworks for Atmospheric Water Harvesting.

Atmospheric water harvesting using reticular materials is an innovation that has the potential to change the world. Using covalent organic frameworks (COFs) for capturing water holds great promise because COFs are metal-free, stable under working conditions, and their structure can be intentionally designed to meet the requirements for this application. To promote the chemistry and use of COFs for atmospheric water harvesting, important features for synthesizing suitable water-harvesting COFs are discussed. The achievements of using COFs as water harvesters are then highlighted, showing how the water harvesting properties are related to the structural design. Finally, perspectives and research directions for further studies in COF chemistry are provided.

High-yield, green and scalable methods for producing MOF-303 for water harvesting from desert air.

Metal-organic frameworks (MOFs) are excellent candidates for water harvesting from desert air. MOF-303 (Al(OH)(PZDC), where PZDC is 1-H-pyrazole-3,5-dicarboxylate), a robust and water-stable MOF, is a particularly promising water-harvesting sorbent that can take up water at low relative humidity and release it under mild heating. Accordingly, development of a facile, high-yield synthesis method for its production at scale is highly desirable. Here we report detailed protocols for the green, water-based preparation of MOF-303 on both gram and kilogram scales. Specifically, four synthetic methods (solvothermal, reflux, vessel and microwave), involving different equipment requirements, are presented to guarantee general accessibility. Typically, the solvothermal method takes ~24 h to synthesize MOF-303, while the reflux and vessel methods can reduce the time to 4-8 h. With the microwave-assisted method, the reaction time can be further reduced to just 5 min. In addition, we provide guidance on the characterization of MOF-303, as well as water-harvesting MOFs in general, to ensure high quality of the product in terms of its purity, crystallinity, porosity and water uptake. Furthermore, to address the need for future commercialization of this material, we demonstrate that our protocol can be employed to produce 3.5 kg per batch with a yield of 91%. MOF-303 synthesized at this large scale shows similar crystallinity and water uptake capacity compared to the respective material produced at a small scale. Our synthetic procedure is green and water-based, and can produce the MOF within hours.

A new mode of luminescence in lanthanide oxalates metal-organic frameworks.

Two lanthanide metal-organic frameworks [Ln-MOFs, Ln = Eu(III), Tb(III)] composed of oxalic acid and Ln building units were hydrothermally synthesized and fully characterized by powder X-ray diffraction, Fourier-transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscope, and energy-dispersive X-ray spectroscopy. Furthermore, their magnetic susceptibility measurements were obtained using SQUID based vibrating sample magnetometer (MPMS 3, Quantum Design). Both Ln-MOFs exhibited highly efficient luminescent property. Solid-state photoluminescence (PL) measurements revealed phosphorescence emission bands of Eu-MOF and Tb-MOF centered at 618 nm (red emission) and 550 nm (green emission) upon excitation at 396 nm and 285 nm, respectively. Eu-MOF and Tb-MOF displayed a phosphorescence quantum yield of 53% and 40%, respectively. Time-resolved PL analyses showed very long lifetime values, at 600 and 1065 ± 1 µs for Eu-MOF and Tb-MOF, respectively. Calculations performed by density functional theory indicated a charge transfer form metal centres to the ligand which was in good agreement with the experimental studies. Therefore, this new mode of highly photoluminescent MOF materials is studied for the first time which paves the way for better understanding of these systems for potential applications.

Hydrazine-Hydrazide-Linked Covalent Organic Frameworks for Water Harvesting.

We report a postsynthetic strategy and its implementation to make covalent organic frameworks (COFs) with irreversible hydrazide linkages. This involved the synthesis of three 2D and 3D hydrazine-linked frameworks and their partial oxidation. The linkage synthesis and functional group transformation-hydrazine and hydrazide-were evidenced by 15N multi-CP-MAS NMR. In addition, the isothermal water uptake profiles of these frameworks were studied, leading to the discovery of one hydrazine-hydrazide-linked COF suitable for water harvesting from air in arid conditions. This COF displayed characteristic S-shaped water sorption profiles, a steep pore-filling step below 18% relative humidity at 25 °C, and a total uptake capacity of 0.45 g g-1. We found that even small changes made on the molecular level can lead to major differences in the water isotherm profiles, therefore pointing to the utility of water sorption analysis as a complementary analytical tool to study linkage transformations.

Zeolite NPO-Type Azolate Frameworks.

Three-membered rings (3-rings) are an important structural motif in zeolite chemistry, but their formation remains serendipitous in reticular chemistry when designing zeolitic imidazolate frameworks (ZIFs). Herein, we report a design principle for constructing four new ZIFs, termed ZIF-1001 to -1004, from tetrahedral ZnII centers (T), benzotriazolate (bTZ), and different functionalized benzimidazolates (RbIM) that adopt a new zeolite NPO-type topology built from 3-rings. Two factors were critical for this discovery: i) incorporating the bTZ linker within the structures formed 3-rings due to a ∠(T-bTZ-T) angle of 120-130° reminiscent of the ∠(Ge-O-Ge) angle (130°) observed in germanate zeolite-type structures having 3-rings; and ii) RbIM guided the coordination chemistry of bTZ to bind preferentially in an imidazolate-type mode. This series' ability to selectively capture CO2 from high-humidity flue gas and trap ethane from tail gas during shale gas extraction was demonstrated.

Metal-Organic Frameworks Can Photocatalytically Split Water-Why Not?

The opinion is provided about the stability and photocatalytic capability of metal-organic frameworks in photocatalytic overall water splitting.

Hexagonal Layer Manganese Metal-Organic Framework for Photocatalytic CO2 Cycloaddition Reaction.

A novel manganese metal-organic framework (Mn-MOF) termed UAEU-50 assembled from a benzenedicarboxylate linker (BDC) and trinuclear manganese clusters was synthesized and fully characterized using different spectroscopic and analytic techniques (e.g., X-ray powder diffraction, UV-vis diffuse reflectance spectroscopy, thermogravimetric analysis, scanning electron microscopy, and energy-dispersive X-ray spectroscopy). UAEU-50 adopted a hexagonal layer structure and exhibited superior thermal stability and robust chemical stability. Photocatalytic activities of UAEU-50 were investigated using the cycloaddition of CO2 to different epoxides, forming cyclic carbonates. Impressively, UAEU-50 can transform up to 90% photocatalytic CO2 conversion to cyclic carbonates in the visible-light region at ambient conditions.

Entanglement of Square Nets in Covalent Organic Frameworks.

Two entangled 2D square covalent organic frameworks (COFs) have been synthesized from 4,4',4″,4‴-(9,9'-spirobi[fluorene]-2,2',7,7'-tetrayl)-tetrabenzaldehhyde (SFTB) and p-phenylenediamine (PPA) and benzidine (BZD) to form COF-38, [(SFTB)(PPA)2]imine, and its isoreticular form COF-39, [(SFTB)(BZD)2]imine. We also report the single-crystal electron diffraction structure of COF-39 and find that it is composed of mutually entangled 2D square nets (sql). These COFs represent the first examples of entangled 2D COF structures, which, as we illustrate, were made possible by our strategy of using the distorted tetrahedral SFTB building unit. SFTB overcomes the propensity of 2D COFs to stack through π-π stacking and allows entanglements to form. This work significantly adds to the design principles of COFs.

A Highly Sensitive and Flexible Metal-Organic Framework Polymer-Based H2S Gas Sensor.

We report the fabrication of a novel metal-organic framework (MOF)-polymer mixed-matrix flexible membrane for the detection of hydrogen sulfide (H2S) gas at room temperature. This high-performance gas sensor is based on MOF-5 microparticles embedded on a conductivity-controlled chitosan (CS) organic membrane. The conductivity of the organic membrane is controlled by blending it with a glycerol ionic liquid (IL) at different concentrations. The sensor showed a remarkable detection sensitivity for H2S gas at a concentrations level as low as 1 ppm at room temperature. The MOF-5/CS/IL gas sensor demonstrates a highly desirable detection selectivity, fast response time (<8 s), recovery time of less than 30 s, and outstanding sensing stability averaging at 97% detection with 50 ppm of H2S gas. This composite having high sensitivity, low-power consumption, and flexibility holds great promise for addressing current challenges pertinent to environmental sustainability.

Reticular design and crystal structure determination of covalent organic frameworks.

Reticular chemistry of covalent organic frameworks (COFs) deals with the linking of discrete organic molecular building units into extended structures adopting various topologies by strong covalent bonds. The past decade has witnessed a rapid development of COF chemistry in terms of both structural diversity and applications. From the structural perspective, irrespective of our subject of concern with regard to COFs, it is inevitable to take into account the structural aspects of COFs in all dimensions from 1D ribbons to 3D frameworks, for which understanding the concepts of reticular chemistry, based mainly on 'reticular design', will seemingly lead to unlimited ways of exploring the exquisiteness of this advanced class of porous, extended, and crystalline materials. A comprehensive discussion and understanding of reticular design, therefore, is of paramount importance so that everyone willing to research on COFs can interpret well and chemically correlate the geometrical structures of this subset of reticular materials and their practical applications. This article lies at the heart of using the conceptual basis of reticular chemistry for designing, modeling, and determination of novel infinite and crystalline structures. Especially, the structure determinations are described by means of chronological advances of discoveries and development of COFs whereby their crystal structures are elucidated by modeling through the topological approach, 3D electron diffraction, single-crystal X-ray diffraction, and powder X-ray diffraction techniques.

3D Covalent Organic Frameworks Selectively Crystallized through Conformational Design.

We present a strategy whereby selective formation of imine covalent organic frameworks (COFs) based on linking of triangles and squares into the fjh topology was achieved by the conformational design of the building units. 1,3,5-Trimethyl-2,4,6-tris(4-formylphenyl)benzene (TTFB, triangle) and 1,1,2,2-tetrakis(4-aminophenyl)ethene (ETTA, square) were reticulated into [(TTFB)4(ETTA)3]imine, termed COF-790, which was fully characterized by spectroscopic, microscopic, and X-ray diffraction techniques. COF-790 exhibits permanent porosity and a Brunauer-Emmett-Teller (BET) surface area of 2650 m2 g-1. Key to the formation of this COF in crystalline form is the pre-designed conformation of the triangle and the square units to give dihedral angles in the range of 75-90°, without which the reaction results in the formation of amorphous product. We demonstrate the versatility of our strategy by also reporting the synthesis and characterization of two isoreticular forms of COF-790, COF-791 and COF-792, based on other square building units.

A Porous Covalent Organic Framework with Voided Square Grid Topology for Atmospheric Water Harvesting.

Atmospheric moisture is a ubiquitous water resource available at any time and any place, making it attractive to develop materials for harvesting water from air to address the imminent water shortage crisis. In this context, we have been exploring the applicability of covalent organic frameworks (COFs) for water harvesting and report here a new porous, two-dimensional imine-linked COF with a voided square grid topology, termed COF-432. Unlike other reported COFs, COF-432 meets the requirements desired for water harvesting from air in that it exhibits an S-shaped water sorption isotherm with a steep pore-filling step at low relative humidity and without hysteretic behavior-properties essential for energy-efficient uptake and release of water. Further, it can be regenerated at ultra-low temperatures and displays exceptional hydrolytic stability, as demonstrated by the retention of its working capacity after 300 water adsorption-desorption cycles.