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Afterglow materials have garnered significant interest due to distinct photophysical characteristics. However, it is still difficult to achieve long afterglow phosphorescence from organic molecules due to aggregation-caused quenching (ACQ) and energy dissipation. In addition, most materials reported so far have long afterglow emission only at room or even low temperatures, and mainly use UV light as an excitation source. In this work, we report a strategy to achieve high temperature long afterglow emission through the assembly of isolated 0D metal-organic cages (MOCs). In which, both ACQ and phosphorescence quenching effects are effectively mitigated by altering the stacking mode of organic chromophores through orthogonally anchoring into the edges of cubic MOCs. Furthermore, improvement in molecular rigidity, promotion of spin-orbit coupling and broadening of the absorption range are achieved through the MOC- engineering strategy. As a result, we successfully synthesized MOCs that can produce afterglow emission even after excitation by WLEDs at high temperatures (380 K). Moreover, the MOCs are capable of generating afterglow emissions when excited by mobile phone flashlight at room temperature. Given these features, the potential applications of MOCs in the visual identification of explosives, information encryption and multicolor display are explored.
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The chirality of metal-organic cages holds enormous potential for novel applications in diverse fields, while it is relatively rare to employ such asymmetric units for the construction of noncentrosymmetric materials. Herein, by self-assembling the 4,4',4''-nitrilotribenzoic acid (H3NBA) with bis(cyclopentadienyl)-zirconium dichloride (Cp2ZrCl2, Cp = η5-C5H5) in different solvent conditions, we have obtained three hierarchical packing modes of metallo-tetrahedra with distinct spatial symmetry groups (designated as Zr-α, Zr-ß, and Zr-γ). Among them, Zr-α employs a simple cubic arrangement and is a common centrosymmetric superstructure, which consists of a pair of equimolar metallo-tetrahedra enantiomers in its unit cell. While Zr-ß results in conglomerates with spontaneous resolution without using any resolving agents, giving rise to two enantiopure entities separately (Zr-ß-P, Zr-ß-M). More importantly, Zr-γ breaks the inversion center of symmetry and crystallizes into a racemic yet non-centrosymmetric superstructure with face-centered cubic packing mode. Based on the non-centrosymmetric nature, the hierarchical superstructure Zr-γ displayed good second harmonic generation activities. This work presents a successful instance wherein the reaction solvent induces the modulation of intermolecular packing mode to afford non-centrosymmetric solid materials, which can greatly promote the development of noncentrosymmetric solid (NCS) materials.
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The fluorination of the central ring of 1,3,5-benzene-tris-(meta-benzoate) (referred to as BTMB) leads to a twisted tritopic linker which reacts with copper(II) ions to assemble into octahedral (pseudospherical) metal-organic cages (MOCs) with paddle-wheel units at their vertices. In this work, the different sphere packings of these MOCs are explored in detail together with their material properties, which closely resemble those of copper-based metal-organic frameworks (MOFs). Theoretical investigations of the linkers are carried out to analyze the energetic barrier imposed by the fluorine substituents to form the observed atropisomers.
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Metal organic cages (MOCs), as an emerging discrete supramolecular compounds, have received widespread attention in separation, biomedicine, gas capture, catalysis, and molecular recognition due to their porosity, adjustability and stability. Herein, we present a new chiral MOC FeII4L4 coated capillary column prepared for gas chromatographic (GC) separation of different types of organic compounds, including n-alkanes, n-alcohols, alkylbenzenes, isomers, especially for racemic compounds. There are 20 different kinds of racemates (e.g., alcohols, ethers, epoxides, esters, alkenes, and aldehydes) were well resolved on the FeII4L4 chiral column and a maximum resolution value for 1-phenyl-1-propanol reaches 6.17. The FeII4L4 coated column exhibited high column efficiency (3100 plates m-1 for n-dodecane) and good enantiomeric resolution complementary to that of a commercial ß-DEX 120 column and the previously reported chiral MOC [Fe4L6] (ClO4)8 coated column. The relative standard deviation (RSDs) of the peak area and retention time of glycidol and nitrotoluene were below 1.2 %. This study reveals that chiral MOCs have good application prospects in chromatographic separation.
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One-step purification of ethylene from ternary mixtures (C2H2, C2H4, and C2H6) can greatly reduce the energy consumption of the separation process, but it is extremely challenging. Herein, we use crystal engineering and reticular chemistry to introduce unsaturated bonds (ethynyl and alkyne) into ligands, and successfully design and synthesized two novel Zr-MOCs (ZrT-1-ethenyl and ZrT-1-alkyne). The introduction of carbon-carbon unsaturated bonds provides abundant adsorption sites within the framework while modulating the pore window size. Comprehensive characterization techniques including single crystal and powder X-ray diffraction, as well as electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) confirm that ZrT-1-ethenyl and ZrT-1-alkyne possess an isostructural framework with ZrT-1 and ZrT-1-Me, respectively. Adsorption isotherms and breakthrough experiments combined with theoretical calculations demonstrate that ZrT-1-ethenyl can effectively remove trace C2H2 and C2H6 in C2H4 and achieve separation of C2H2 from C2H4 and CO2. ZrT-1-ethenyl can also directly purify C2H4 in liquid solutions. This work provides a benchmark for MOCs that one-step purification of ethylene from ternary mixtures.
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Poly-[n]-catenanes (PCs) self-assembled of three-dimensional (3D) metal organic cages (MOCs) (hereafter referred to as PCs-MOCs) are a relatively new class of mechanically interlocked molecules (MIMs) that combine the properties of MOCs and polymers. The synthesis of PCs-MOCs is challenging because of the difficulties associated with interlocking MOCs, the occurrence of multiple weak supramolecular electrostatic interactions between cages, and the importance of solvent templating effects. The high density of mechanical bonds interlocking the MOCs endows the MOCs with mechanical and physical properties such as enhanced stability, responsive dynamic behavior and low solubility, which can unlock new functional properties. In this Minireview, we highlight the benefit of interlocking MOCs in the formation of PCs-MOCs structures as well as the synthetic approaches exploited in their preparation, from thermodynamic to kinetic methods, both in the solution and solid-states. Examples of PCs-MOCs self-assembled from various types of nanosized cages (i.e., tetrahedral, trigonal prismatic, octahedral and icosahedral) are described in this article, providing an overview of the research carried out in this area. The focus is on the structure-property relationship with examples of functional applications such as electron conductivity, X-ray attenuation, gas adsorption and molecular sensing. We believe that the structural and functional aspects of the reviewed PCs-MOCs will attract chemists in this research field with great potential as new functional materials in nanotechnological disciplines such as gas adsorption, sensing and photophysical properties such as X-ray attenuation or electron conductivity.
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A series of metal-organic cages featuring two stereogenic elements, in terms of the twisting of amide moieties within the ligand backbones and the rotation of diazaanthracene segments along the ligand ridges, were exploited. These two chiral components are correlative and serve as relays for transmitting chirality information between the internal and external cages. The chirality information induced by a chiral guest inside the cage cavity can pass through the cage framework and influence the orientation of the diazaanthracene segments on the periphery of the cage. In turn, the chirality of a stereogenic center within the diazaanthracene segments can transfer back into the cavity, enabling discrimination of enantiomeric guests.
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Metal-organic frameworks (MOFs) and metal-organic cages (MOCs) have garnered significant attention as promising photocatalysts due to their tunable chemical structures and integrated multifunctionality. To increase the photocatalytic efficiency, strategies like ligand functionalization, introducing additional catalytic sites, and doping or encapsulating photosensitizers have been explored for both MOFs and MOCs. This concept review focuses on recent advancements in utilizing MOFs and MOCs for photocatalytic hydrogen production, highlighting their unique characteristics and introducing their respective mechanisms in this field. Moreover, it outlines the current challenges and prospects faced by MOFs and MOCs, offering an outlook on their future in this domain.
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The ability to collectively program chiral recognition and the hierarchical self-assembly of molecular and supramolecular building blocks into complex higher-order superstructures is a significant goal in supramolecular chemistry. Metal-organic cages are excellent model systems to examine chiral self-sorting and build hierarchical self-assembly. Herein, details on how limiting the conformational flexibility and incorporating hydrogen bonding functional groups in the ligands can influence chiral self-sorting and hierarchical self-assembly of metal-organic cages are reported. The urea-functionalized axially chiral bis-pyridyl ligands afford high-fidelity in chiral self-sorting in Pd2L4 cages, when they have fewer conformations. Ligand L1, with more conformations, affords mixture of heterochiral and homochiral cages (≈70:30). Among them, the heterochiral cage adopts unusual twisted conformation and self-assembles into 2D sheets, linked by anion coordination between urea and nitrate. Ligand L2, with fewer conformations, affords homochiral cages via high-fidelity chiral self-sorting. The choice of counter anions influences further self-sorting in the solid state: racemate with PF6 - and spontaneously resolves conglomerate with BF4 -. Urea-BF4 hydrogen bonding directs hierarchical self-assembly of the Pd2L4 metal-organic cages into super-cubic networks. The study introduces a new approach in hierarchical self-assembly of metal-organic cages into higher-order networks aided by hydrogen bonding anion coordination with functional ligands.
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We report a series of coordination cages that incorporate peptide chains at their vertices, prepared through subcomponent self-assembly. Three distinct heterochiral tripeptide subcomponents were incorporated, each exhibiting an L-D-L stereoconfiguration. Through this approach, we prepared and characterized three tetrahedral metal-peptide cages that incorporate thiol and methylthio groups. The gelation of these cages was probed through the binding of additional metal ions, with the metal-peptide cages acting as junctions, owing to the presence of sulfur atoms on the peripheral peptides. Gels were obtained with cages bearing cysteine at the C-terminus. Our strategy for developing functional metal-coordinated supramolecular gels with a modular design may result in the development of materials useful for chemical separations or drug delivery.
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Cisteína , Géis , Peptídeos , Cisteína/química , Peptídeos/química , Géis/química , Íons/química , Metais/química , Complexos de Coordenação/químicaRESUMO
The field of molecular cages has attracted increasing interest in relation to the development of biological applications, as evidenced by the remarkable examples published in recent years. Two key factors have contributed to this achievement: First, the remarkable and adjustable host-guest chemical properties of molecular cages make them highly suitable for biological applications. This allows encapsulating therapeutic molecules to improve their properties. Second, significant advances have been made in synthetic methods to create water-soluble molecular cages. Achieving the necessary water solubility is a significant challenge, which in most cases requires specific chemical groups to overcome the inherent hydrophobic nature of the molecular cages which feature the organic components of the cage. This can be achieved by either incorporating water-solubilizing groups with negative/positive charges, polyethylene glycol chains, etc.; or by introducing charges directly into the cage structure itself. These synthetic strategies allow preparing water-soluble molecular cages for diverse biological applications, including cages' anticancer activity, anticancer drug delivery, photodynamic therapy, and molecular recognition of biological molecules. In the review we describe selected examples that show the main concepts to achieve water solubility in molecular cages and some selected recent biological applications.
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Sistemas de Liberação de Medicamentos , Fotoquimioterapia , Polietilenoglicóis , ÁguaRESUMO
Integrating the advantages of homogeneous and heterogeneous catalysis has proved to be an optimal strategy for developing catalytic systems with high efficiency, selectivity, and recoverability. Supramolecular metal-organic cages (MOCs), assembled by the coordination of metal ions with organic linkers into discrete molecules, have performed solvent processability due to their tunable packing modes, endowing them with the potential to act as homogeneous or heterogeneous catalysts in different solvent systems. Here, the design and synthesis of a series of stable {Cu3} cluster-based tetrahedral MOCs with varied packing structures are reported. These MOCs, as homogeneous catalysts, not only show high catalytic activity and selectivity regardless of substrate size during the CO2 cycloaddition reaction, but also can be easily recovered from the reaction media through separating products and co-catalysts by one-step work-up. This is because that these MOCs have varied solubilities in different solvents due to the tunable packing of MOCs in the solid state. Moreover, the entire catalytic reaction system is very clean, and the purity of cyclic carbonates is as high as 97% without further purification. This work provides a unique strategy for developing novel supramolecular catalysts that can be used for homogeneous catalysis and recycled in a heterogeneous manner.
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The self-assembled metal-organic cages (MOCs) have been evolved as a paradigm of enzyme-mimic catalysts since they are able to synergize multifunctionalities inherent in metal and organic components and constitute microenvironments characteristic of enzymatic spatial confinement and versatile host-guest interactions, thus facilitating unconventional organic transformations via unique driving-forces such as weak noncovalent binding and electron/energy transfer. Recently, MOC-based photoreactors emerged as a burgeoning platform of supramolecular photocatalysis, displaying anomalous reactivities and selectivities distinct from bulk solution. This perspective recaps two decades journey of the photoinduced radical reactions by using photoactive metal-organic cages (PMOCs) as artificial reactors, outlining how the cage-confined photocatalysis was evolved from stoichiometric photoreactions to photocatalytic turnover, from high-energy UV-irradiation to sustainable visible-light photoactivation, and from simple radical reactions to multi-level chemo- and stereoselectivities. We will focus on PMOCs that merge structural and functional biomimicry into a single-cage to behave as multi-role photoreactors, emphasizing their potentials in tackling current challenges in organic transformations through single-electron transfer (SET) or energy transfer (EnT) pathways in a simple, green while feasible manner.
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Piezocatalytic hydrogen peroxide (H2 O2 ) production is a green synthesis method, but the rapid complexation of charge carriers in piezocatalysts and the difficulty of adsorbing substrates limit its performance. Here, metal-organic cage-coated gold nanoparticles are anchored on graphitic carbon nitride (MOC-AuNP/g-C3 N4 ) via hydrogen bond to serve as the multifunctional sites for efficient H2 O2 production. Experiments and theoretical calculations prove that MOC-AuNP/g-C3 N4 simultaneously optimize three key parts of piezocatalytic H2 O2 production: i) the MOC component enhances substrate (O2 ) and product (H2 O2 ) adsorption via host-guest interaction and hinders the rapid decomposition of H2 O2 on MOC-AuNP/g-C3 N4 , ii) the AuNP component affords a strong interfacial electric field that significantly promotes the migration of electrons from g-C3 N4 for O2 reduction reaction (ORR), iii) holes are used for H2 O oxidation reaction (WOR) to produce O2 and H+ to further promote ORR. Thus, MOC-AuNP/g-C3 N4 can be used as an efficient piezocatalyst to generate H2 O2 at rates up to 120.21â µmol g-1 h-1 in air and pure water without using sacrificial agents. This work proposes a new strategy for efficient piezocatalytic H2 O2 synthesis by constructing multiple active sites in semiconductor catalysts via hydrogen bonding, by enhancing substrate adsorption, rapid separation of electron-hole pairs and preventing rapid decomposition of H2 O2 .
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Metal-organic cages (MOCs) have garnered significant attention due to their unique discrete structures, intrinsic porosity, designability, and tailorability. However, weak inter-cage interactions, such as van der Waals forces and hydrogen bonding can cause solid-state MOCs to lose structural integrity during desolvation, leading to the loss of porosity. In this work, a novel strategy to retain the permanent porosity of Cu-paddlewheel-based MOCs, enabling their use as heterogeneous catalysts is presented. Post-synthetic solvothermal treatments in non-coordinating solvents, mesitylene, and p-xylene, effectively preserve the packing structures of solvent-evacuated MOCs while preventing cage agglomeration. The resulting MOCs exhibit an exceptional N2 sorption capacity, with a high surface area (SBET = 1934 m2 g-1 for MOP-23), which is among the highest reported for porous MOCs. Intriguingly, while the solvothermal treatment reduced Cu(II) to Cu(I) in the Cu-paddlewheel clusters, the MOCs with mixed-valenced Cu(I)/Cu(II) maintained their crystallinity and permanent porosity. The catalytic activities of these MOCs are successfully examined in copper(I)-catalyzed hydrative amide synthesis, highlighting the prospect of MOCs as versatile reaction platforms.
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Controlling the coordination sphere of heterogeneous single-metal-site catalysts is a powerful strategy for fine-tuning their catalytic properties but is fairly difficult to achieve. To address this problem, we immobilized supramolecular cages where the primary- and secondary coordination sphere are controlled by ligand design. The kinetics of these catalysts were studied in a model reaction, the hydrolysis of ammonia borane, over a temperature range using fast and precise online measurements generating high-precision Arrhenius plots. The results show how catalytic properties can be enhanced by placing a well-defined reaction pocket around the active site. Our fine-tuning yielded a catalyst with such performance that the reaction kinetics are diffusion-controlled rather than chemically controlled.
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A perylene diimide-based metal-organic cage (MOC4c) was found to be an efficient transmembrane transporter for ions and small molecules through the internal cavity of the cage. MOC4c could selectively transport different anions, as evidenced by vesicle-based fluorescenceassays and planar lipid bilayer-based current recordings.Furthermore, MOC4c appears tofacilitate calcein transport across the lipid bilayer membrane of a livingcell, suggesting that MOC4c could be used as a biologicaltool for small molecule drugstransmembrane transportation.
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Photocatalytic synthesis of hydrogen peroxide (H2 O2 ) is a potential clean method, but the long distance between the oxidation and reduction sites in photocatalysts hinders the rapid transfer of photogenerated charges, limiting the improvement of its performance. Here, a metal-organic cage photocatalyst, Co14 (L-CH3 )24 , is constructed by directly coordinating metal sites (Co sites) used for the O2 reduction reaction (ORR) with non-metallic sites (imidazole sites of ligands) used for the H2 O oxidation reaction (WOR), which shortens the transport path of photogenerated electrons and holes, and improves the transport efficiency of charges and activity of the photocatalyst. Therefore, it can be used as an efficient photocatalyst with a rate of as high as 146.6â µmol g-1 h-1 for H2 O2 production under O2 -saturated pure water without sacrificial agents. Significantly, the combination of photocatalytic experiments and theoretical calculations proves that the functionalized modification of ligands is more conducive to adsorbing key intermediates (*OH for WOR and *HOOH for ORR), resulting in better performance. This work proposed a new catalytic strategy for the first time; i.e., to build a synergistic metal-nonmetal active site in the crystalline catalyst and use the host-guest chemistry inherent in the metal-organic cage (MOC)to increase the contact between the substrate and the catalytically active site, and finally achieve efficient photocatalytic H2 O2 synthesis.
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As an emerging subset of organic complexes, metal complexes have garnered considerable attention owing to their outstanding structures, properties, and applications. In this content, metal-organic cages (MOCs) with defined shapes and sizes provide internal spaces to isolate water for guest molecules, which can be selectively captured, isolated, and released to achieve control over chemical reactions. Complex supramolecules are constructed by simulating the self-assembly behavior of the molecules or structures in nature. For this purpose, massive amounts of cavity-containing supramolecules, such as metal-organic cages (MOCs), have been extensively explored for a large variety of reactions with a high degree of reactivity and selectivity. Because sunlight and water are necessary for the process of photosynthesis, water-soluble metal-organic cages (WSMOCs) are ideal platforms for photo-responsive stimulation and photo-mediated transformation by simulating photosynthesis due to their defined sizes, shapes, and high modularization of metal centers and ligands. Therefore, the design and synthesis of WSMOCs with uncommon geometries embedded with functional building units is of immense importance for artificial photo-responsive stimulation and photo-mediated transformation. In this review, we introduce the general synthetic strategies of WSMOCs and their applications in this sparking field.
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Three new ligands containing a bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxydiimide unit have been used to assemble lantern-type metal-organic cages with the general formula [Cu4 L4 ]. Functionalisation of the backbone of the ligands leads to distinct crystal packing motifs between the three cages, as observed with single-crystal X-ray diffraction. The three cages vary in their gas sorption behaviour, and the capacity of the materials for CO2 is found to depend on the activation conditions: softer activation conditions lead to superior uptake, and one of the cages displays the highest BET surface area found for lantern-type cages so far.