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Membrane-based enantioselective separation is a promising method for chiral resolution due to its low cost and high efficiency. However, scalable fabrication of chiral separation membranes displaying both high enantioselectivity and high flux of enantiomers is still a challenge. Here, the authors report the preparation of homochiral porous organic cage (Covalent cage 3 (CC3)-R)-based enantioselective thin-film-composite membranes using polyamide (PA) as the matrix, where fully organic and solvent-processable cage crystals have good compatibility with the polymer scaffold. The hierarchical CC3-R channels consist of chiral selective windows and inner cavities, leading to favorable chiral resolution and permeation of enantiomers; the CC3-R/PA composite membranes display an enantiomeric excess of 95.2% for R-(+)-limonene over S-(-)-limonene and a high flux of 99.9 mg h-1 m-2. This work sheds light on the use of homochiral porous organic cages for preparing enantioselective membranes and demonstrates a new route for the development of next-generation chiral separation membranes.

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Two crystalline large-sized porous organic cages (POCs) based on conical calix[4]arene (C4A) were designed and synthesized. The four-jaw C4A unit tends to follow the face-directed self-assembly law with the planar triangular building blocks such as tris(4-aminophenyl)amine (TAPA) or 1,3,5-tris(4-aminophenyl)benzene (TAPB) to generate a predictable cage with a stoichiometry of [6+8]. The formation of the large cages is confirmed through their relative molecular mass measured using MALDI-TOF/TOF spectra. The protonated molecular ion peaks of C4A-TAPA and C4A-TAPB were observed at m/z 5109.0 (calculated for C336H240O24N32: m/z 5109.7) and m/z 5594.2 (calculated for C384H264O24N24: m/z 5598.4). C4A-POCs exhibit I-type N2 adsorption-desorption isotherms with the BET surface areas of 1444.9 m2 ⋅ g-1 and 1014.6 m2 ⋅ g-1. The CO2 uptakes at 273 K are 62.1 cm3 ⋅ g-1 and 52.4 cm3 ⋅ g-1 at a pressure of 100 KPa. The saturated iodine vapor static uptakes at 348 K are 3.9 g ⋅ g-1 and 3.5 g ⋅ g-1. The adsorption capacity of C4A-TAPA for SO2 reaches to 124.4 cm3 ⋅ g-1 at 298 K and 1.3 bar. Additionally, the adsorption capacities of C4A-TAPA for C2H2, C2H4, and C2H6 were evaluated.

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Piezochromic materials that exhibit pressure-dependent luminescence variations are attracting interest with wide potential applications in mechanical sensors, anticounterfeiting and storage devices. Crystalline porous materials (CPMs) have been widely studied in piezochromism for highly tunable luminescence. Nevertheless, reversible and high-contrast emission response with a wide pressure range is still challenging. Herein, the first example of hierarchical porous cage-based πOF (Cage-πOF-1) with spring structure was synthesized by using aromatic chiral cages as building blocks. Its elastic properties evaluated based on the bulk modulus (9.5 GPa) is softer than most reported CPMs and the collapse point (20.0 GPa) significantly exceeds ever reported CPMs. As smart materials, Cage-πOF-1 displays linear pressure-dependent emission and achieves a high-contrast emission difference up to 154 nm. Pressure-responsive limit is up to 16 GPa, outperforming the CPMs reported so far. Dedicated experiments and density functional theory (DFT) calculations illustrate that π-π interactions-dominated controllable structural shrinkage and porous-spring-structure-mediated elasticity is responsible for the outstanding piezofluorochromism.

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Molecular separations involving solvents and organic impurities represent great challenges for environmental and water-intensive industries. Novel materials with intrinsic nanoscale pores offer a great choice for improvement in terms of energy efficiency and capital costs. Particularly, in applications where gradient and ordered separation of organic contaminants remain elusive, smart materials with switchable pores can offer efficient solutions. Here, we report a hierarchically networked porous organic cage membrane with dynamic control over pores, elucidating stable solvent permeance and tunable dye rejection over different molecular weights. The engineered cage membrane can spontaneously modulate its geometry and pore size from water to methanol and DMF in a reversible manner. The cage membrane exhibits ≥585.59 g mol-1 molecular weight cutoff preferentially in water and is impeded by methanol (799.8 g mol-1) and DMF (≈1017 g mol-1), reflecting 36 and 73% change in rejection due to self-regulation and the flexible network, respectively. Grazing incidence X-ray diffraction illustrates a clear peak downshift, suggesting an intrinsic structural change when the cage membranes were immersed in methanol or DMF. We have observed reversible structural changes that can also be tuned by preparing a methanol/DMF mixture and adjusting their ratio, thereby enabling gradient molecular filtration. We anticipate that such cage membranes with dynamic selectivity could be promising particularly for industrial separations and wastewater treatment.

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Chiral induction has been an important topic in chemistry, not only for its relevance in understanding the mysterious phenomenon of spontaneous symmetry breaking in nature but also due to its critical implications in medicine and the chiral industry. The induced chirality of fullerenes by host-guest interactions has been rarely reported, mainly attributed to their chiral resistance from high symmetry and challenges in their accessibility. Herein, we report two new pairs of chiral porous aromatic cages (PAC), R-PAC-2, S-PAC-2 (with Br substituents) and R-PAC-3, S-PAC-3 (with CH3 substituents) enantiomers. PAC-2, rather than PAC-3, achieves fullerene encapsulation and selective binding of C70 over C60 in fullerene carbon soot. More significantly, the occurrence of chiral induction between R-PAC-2, S-PAC-2 and fullerenes is confirmed by single-crystal X-ray diffraction and the intense CD signal within the absorption region of fullerenes. DFT calculations reveal the contribution of electrostatic effects originating from face-to-face arene-fullerene interactions dominate C70 selectivity and elucidate the substituent effect on fullerene encapsulation. The disturbance from the differential interactions between fullerene and surrounding chiral cages on the intrinsic highly symmetric electronic structure of fullerene could be the primary reason accounting for the induced chirality of fullerene.

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In this work, homochiral reduced imine cage was covalently bonded to the surface of the silica to prepare a novel high-performance liquid chromatography stationary phase, which was applied for the multiple separation modes such as normal phase, reversed-phase, ion exchange, and hydrophilic interaction chromatography. The successful preparation of the homochiral reduced imine cage bonded silica stationary phase was confirmed by performing a series of methods including X-ray photoelectron spectroscopy, thermogravimetric analysis, and infrared spectroscopy. From the extracted results of the chiral resolution in normal phase and reversed-phase modes, it was demonstrated that seven chiral compounds were successfully separated, among which the resolution of 1-phenylethanol reached the value of 3.97. Moreover, the multifunctional chromatographic performance of the new molecular cage stationary phase was systematically investigated in the modes of reversed-phase, ion exchange, and hydrophilic interaction chromatography for the separation and analysis of a total of 59 compounds in eight classes. This work demonstrated that the homochiral reduced imine cage not only achieved multiseparation modes and multiseparation functions performance with high stability, but also expanded the application of the organic molecular cage in the field of liquid chromatography.

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The nuclear industry will continue to develop rapidly and produce energy in the foreseeable future; however, it presents unique challenges regarding the disposal of released waste radionuclides because of their volatility and long half-life. The release of radioactive isotopes of iodine from uranium fission reactions is a challenge. Although various adsorbents have been explored for the uptake of iodine, there is still interest in novel adsorbents. The novel adsorbents should be synthesized using reliable and economically feasible synthetic procedures. Herein, we discussed the state-of-the-art performance of various categories of porous organic materials including covalent organic frameworks, covalent triazine frameworks, porous aromatic frameworks, porous organic cages, among other porous organic polymers for the uptake of iodine. This review discussed the synthesis of porous organic materials and their iodine adsorption capacity and reusability. Finally, the challenges and prospects for iodine capture using porous organic materials are highlighted.

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We report a new composite material consisting of silver nanoparticles decorated with three-dimensional molecular organic cages based on light-absorbing porphyrins. The porphyrin cages serve to both stabilize the particles and allow diffusion and trapping of small molecules close to the metallic surface. Combining these two photoactive components results in a Fano-resonant interaction between the porphyrin Soret band and the nanoparticle-localised surface-plasmon resonance. Time-resolved spectroscopy revealed the silver nanoparticles transfer up to 37 % of their excited-state energy to the stabilising layer of porphyrin cages. These unusual photophysics cause a 2-fold current increase in photoelectrochemical water-splitting measurements. The composite structure provides a compelling proof of concept for advanced photosensitiser systems with intrinsic porosity for photocatalytic and sensing applications.

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Incorporating metal nanoparticles (MNPs) into porous composites with controlled size and spatial distributions is beneficial for a broad range of applications, but it remains a synthetic challenge. Here, we present a method to immobilize a series of highly dispersed MNPs (Pd, Ir, Pt, Rh, and Ru) with controlled size (<2 nm) on hierarchically micro- and mesoporous organic cage supports. Specifically, the metal-ionic surfactant complexes serve as both metal precursors and mesopore-forming agents during self-assembly with a microporous imine cage CC3, resulting in a uniform distribution of metal precursors across the resultant supports. The functional heads on the ionic surfactants as binding sites, together with the nanoconfinement of pores, guide the nucleation and growth of MNPs and prevent their agglomeration after chemical reduction. Moreover, the as-synthesized Pd NPs exhibit remarkable activity and selectivity in the tandem reaction due to the advantages of ultrasmall particle size and improved mass diffusion facilitated by the hierarchical pores.

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A continuous flow methodology for the facile and high-yielding synthesis of the porphyrin-based self-assembled organic cage, P12 L24 is reported, along with the serendipitous discovery of a kinetic product, P9 L18 cage, which has been characterized by MALDI-TOF MS, NMR, and AFM analysis. A theoretical study suggests a tricapped trigonal prismatic geometry for P9 L18 . Unlike P12 L24 , P9 L18 is unstable and readily decomposes into monomers and small oligomers. While the batch synthesis produces only the thermodynamic product P12 L24 , the continuous flow process generates not only the thermodynamic product but also kinetic products, such as P9 L18 , illustrating the advantages of the continuous flow process for the synthesis of self-assembled cages and the exploration of new non-equilibrium assemblies.

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Hydrogen sulfide (H2S) and nitric oxide (NO) are especially known as toxic and polluting gases, yet they are also endogenously produced and play key roles in numerous biological processes. These two opposing aspects of the gases highlight the need for new types of materials to be developed in addition to the most common materials such as activated carbons and zeolites. Herein, a new imine-linked polymer organic framework was obtained using the inexpensive and easy-to-access reagents isophthalaldehyde and 2,4,6-triaminopyrimidine in good yield (64%) through the simple and catalyst-free Schiff-base reaction. The polymeric material has microporosity, an ABET surface area of 51 m2/g, and temperature stability up to 300 °C. The obtained 2,4,6-triaminopyrimidine imine-linked polymer organic material has a higher capacity to adsorb NO (1.6 mmol/g) than H2S (0.97 mmol/g). Release studies in aqueous solution showed that H2S has a faster release (3 h) from the material than NO, for which a steady release was observed for at least 5 h. This result is the first evaluation of the possibility of an imine-linked polymer organic framework being used in the therapeutic release of NO or H2S.

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Porous molecular materials are constructed from molecules that assemble in the solid-state such that there are cavities or an interconnected pore network. It is challenging to control the assembly of these systems, as the interactions between the molecules are generally weak, and subtle changes in the molecular structure can lead to vastly different intermolecular interactions and subsequently different crystal packing arrangements. Similarly, the use of different solvents for crystallization, or the introduction of solvent vapour, can result in different polymorphs and pore networks being formed. It is difficult to uniquely describe the pore networks formed, and thus we analyse 1033 crystal structures of porous molecular systems to determine the underlying topology of their void spaces and potential guest diffusion networks. Material-agnostic topology definitions are applied. We use the underlying topological nets to examine whether it is possible to apply isoreticular design principles to porous molecular materials. Overall, our automatic analysis of a large dataset gives a general insight into the relationships between molecular topologies and the topological nets of their pore network. We show that while porous molecular systems tend to pack similarly to non-porous molecules, the topologies of their pore distributions resemble those of more prominent porous materials, such as metal-organic frameworks and covalent organic frameworks.

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The controlled synthesis of subnanometer-sized metal clusters (MCs) presents a fascinating prospect for the research of size-dependent properties. In this study, a facile approach by employing porous racemic organic cage crystals as supports for immobilizing a broad range of noble MCs (e.g., Ru, Ir, Rh) is reported. Downsizing the support to the nanoscale leads to resultant MCs with precisely controlled sizes < 0.7 nm. Such enhanced stabilization ability is a result of enhanced metal-support interactions as well as the nanoconfinement of organic cages in controlling the growth of MCs. Moreover, the obtained MCs display excellent catalytic performance in a series of liquid-phase reactions owing to a decrease in the diffusion resistance from the substrate to MCs immobilized by the nano-sized cage support.

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Anthropogenic greenhouse gases contribute to global warming. Among those gases, perfluorocarbons (PFCs) are thousands to tens of thousands of times more harmful to the environment than comparable amounts of carbon dioxide. To date, materials that selectively adsorb perfluorocarbons in favor of other less harmful gases have not been reported. Here, a series of porous organic cage compounds with alkyl-, fluoroalkyl-, and partially fluorinated alkyl groups is presented. Their isomorphic crystalline states allow the study of the structure-property relationship between the degree of fluorination of the alkyl chains and the gas sorption properties for PFCs and their selective uptakes in comparison to other, nonfluorinated gases. By this approach, one compound having superior selectivities of PFCs versus N2 or CO2 under ambient conditions is identified.

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Living systems use chemical fuels to transiently assemble functional structures. As a step toward constructing abiotic mimics of such structures, we herein describe dissipative formation of covalent basket cage CBC 5 by reversible imine condensation of cup-shaped aldehyde 2 (i.e., basket) with trivalent aromatic amine 4. This nanosized [4+4] cage (V=5 nm3 , Mw =6150 Da) has shape of a truncated tetrahedron with four baskets at its vertices and four aromatic amines forming the faces. Importantly, tris-aldehyde basket 2 and aliphatic tris-amine 7 undergo condensation to give small [1+1] cage 6. The imine metathesis of 6 and aromatic tris-amine 4 into CBC 5 was optimized to bias the equilibrium favouring 6. Addition of tribromoacetic acid (TBA) as a chemical fuel perturbs this equilibrium to result in the transient formation of CBC 5, with subsequent consumption of TBA via decarboxylation driving the system back to the starting state.

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HYPOTHESIS: Although it is well-accepted that iron oxide nanoparticles are considered as artificial enzymes when their surface is hydrophilic, the enzyme-like properties of iron oxide nanoparticles with hydrophobic surface coating is unexplored. This work demonstrates that hydrophobic iron oxide nanocrystals coated with a layer of oleic acid could serve as artificial enzymes when their surface is covered by a layer of ionic surfactant. Furthermore, the co-assembly of iron oxide nanocrystals and porous organic cages could modulate their enzyme-like activities. EXPERIMENTS: Co-assembly of iron oxide (Fe3O4) nanocrystals with different size and porous organic cages (POCs) was performed by an emulsion-confined strategy to achieve hybridized Fe3O4/POCs co-assemblies. The peroxidase-mimic activity of these co-assemblies were assessed in the presence of 3, 3', 5, 5'-Tetramethylbenzidine (TMB) and hydrogen peroxide. Finally, these co-assemblies were applied as sensors to detect glucose and hydrogen peroxide. FINDINGS: Co-assembly of Fe3O4 nanocrystals and POCs resulted in the self-assembly of Fe3O4 nanoparticles into two-dimensional nanoparticle superlattices on the eight (111) facets of the octahedral POCs colloidal crystals. The unique oil-in-water (O/W) emulsion confined assembly method switches the Fe3O4 nanoparticles and POC crystals from hydrophobic to hydrophilic because of the strong hydrophobic interactions. Importantly, these co-assemblies dispersed in water showed strong peroxidase-mimic activity in water despite that their surface is covered by a bilayer of aliphatic chains. Furthermore, the intrinsic enzymatic activity of the co-assemblies is highly dependent on the size of the nanocrystals, and a higher catalytic activity is achieved from a larger sized Fe3O4 nanocrystal.

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Capillary electrochromatography for enantioseparation has received considerable research attention in the past decades, because it integrates the advantages of classical electrophoresis and modern micro-column separation. Chirality is a fundamental feature of compounds found in nature and is also a major concern in the modern pharmaceutical industry. Porous organic cages (POCs) are defined as a class of porous materials with permanent ordered three-dimensional cavity structures that are different from those of porous materials, such as zeolite, metal-organic frameworks, covalent organic frameworks, and mesoporous silica. POCs have good solubility in general organic solvents and can be used as a chromatographic stationary phase conveniently coated inside a standard capillary column. Homochiral POCs with hydroxyl groups on the cage molecules were synthesized by imine-linked condensation of 2-hydroxy-1,3,5-triformylbenzene with (1R,2R)-1,2-diphenylethylenediamine. The thus-synthesized POCs were characterized by nuclear magnetic resonance (NMR) spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, X-ray powder diffraction (XRD) analysis, etc. In the FT-IR spectra, the absorption peaks at 1602, 1489, and 1458 cm-1 were attributed to the C=C-H and C=C tensile vibrations in the benzene ring. The strong characteristic absorption peak at 1636 cm-1 was attributed to the imine bond (C=N) stretching, the two peaks at about 2900 cm-1 were attributed to C-H bond vibration, and the absorption peak at 3420 cm-1 was attributed to the O-H pulling vibration. In the XRD patterns, the powder diffraction peaks of the POCs were consistent with the simulated data. These results indicated that POCs were successfully synthesized. Thermogravimetric analysis was performed in the temperature range of 25-800 ℃ (10 ℃/min), and the POCs were found to be stable up to 380 ℃. Dichloromethane was used as solvent to uniformly coat POCs on the capillary wall to prepare an electrochromatography column. Joule heat generated in electrophoresis was negligible under the experiment condition used for the open-tubular column. Four chiral compounds, viz. dihydroflavone, praziquantel, naproxen, and 3,5-dinitro-N-(1-phenylethyl)benzamide, were used as test compounds, and the electrochromatography separation conditions were optimized such that the best separations were obtained. The voltage was applied to separate the selected enantiomers in the range of 10-20 kV. Considering the good separation and appropriate migration time simultaneously, applied voltages of 13 kV and 12 kV were recommended for dihydroflavones and 3,5-dinitro-N-(1-phenylethyl)benzamide, respectively, as well as 14 kV for praziquantel and naproxen. The concentration of the buffer solution for dihydroflavonoids was 0.075 mol/L, and those for praziquantel, naproxen, and 3,5-dinitro-N-(1-phenylethyl)benzamide were 0.100 mol/L. The pH was 3.51 for all four substances. Resolutions of 2.99, 2.10, 2.58, and 3.59 were achieved on a POC chiral column for dihydroflavonoids, praziquantel, naproxen, and 3,5-dinitro-N-(1-phenylethyl)benzamide, respectively. Two positional isomers, viz. o,m,p-nitrophenol and o,m,p-nitrophenilamine, were also successfully separated with 0.100 mol/L Tris-H3PO4 at pH 3.51. Therefore, the chiral electrochromatography column showed good chiral recognition ability and the POC is an excellent separation material with excellent application prospect in chiral electrochromatography.

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Electroreduction of CO2 into valuable fuels and feedstocks offers a promising way for CO2 utilization. However, the commercialization is limited by the low productivity. Here, we report a strategy to enhance the productivity of CO2 electroreduction by improving diffusion of CO2 to the surface of catalysts using porous organic cages (POCs) as an additive. It was noted that the Faradaic efficiency (FE) of C2+ products could reach 76.1 % with a current density of 1.7 A cm-2 when Cu-nanorod(nr)/CC3 (one of the POCs) was used, which were much higher than that using Cu-nr. Detailed studies demonstrated that the hydrophobic pores of CC3 can adsorb a large amount of CO2 for the reaction, and the diffusion of CO2 in the CC3 to the nanocatalyst surface is easier than that in the liquid electrolyte. Thus, more CO2 molecules make contact with the nanocatalysts in the presence of CC3, enhancing CO2 reduction and inhibiting generation of H2 .

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Thin films with effective ion sieving ability are highly desired in energy storage and conversion devices, including batteries and fuel cells. However, it remains challenging to design and fabricate cost-effective and easy-to-process ultrathin films for this purpose. Here, we report a 300 nm-thick functional layer based on porous organic cages (POCs), a new class of porous molecular materials, for fast and selective ion transport. This solution processable material allows for the design of thin films with controllable thickness and tunable porosity by tailoring cage chemistry for selective ion separation. In the prototype, the functional layer assembled by CC3 can selectively sieve Li+ ions and efficiently suppress undesired polysulfides with minimal sacrifice for the system's total energy density. Separators modified with POC thin films enable batteries with good cycle performance and rate capability and offer an attractive path toward the development of future high-energy-density energy storage devices.

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Capture, storage and subsequent controlled release or transformation of sulfur dioxide (SO2 ) in mild conditions is still a challenge in the material science field. Recent advances in the use of porous materials have demonstrated good SO2 capture, particularly in metal-organic frameworks (MOFs), metal-organic cages (MOCs), and porous organic cages (POCs). The striking feature of these porous materials is the high SO2 uptake capacity in reversible settings. A partially fluorinated MIL-101(Cr) is stand-alone material with the highest SO2 uptake in chemically stable MOFs. Likewise, metal-free adsorbents like POCs exhibits a reversible SO2 uptake behavior. The SO2 adsorption characteristics of these three structurally and functionally unique adsorbent systems are highly dependent on the binding sites and mode of binding of SO2 molecules. This Review has highlighted the preferential binding sites in these materials to give a full perspective on the field. We anticipate that it will offer valuable information on the progress made towards improving SO2 capture by hybrid systems.