Porous Organic Cages

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4602 - 4634

Опубликована: Апрель 6, 2023

Porous organic cages (POCs) are a relatively new class of low-density crystalline materials that have emerged as versatile platform for investigating molecular recognition, gas storage and separation, proton conduction, with potential applications in the fields porous liquids, highly permeable membranes, heterogeneous catalysis, microreactors. In common extended structures, such metal–organic frameworks (MOFs), covalent (COFs), polymers (POPs), POCs possess all advantages specific surface areas, porosities, open pore channels, tunable structures. addition, they discrete structures exhibit good to excellent solubilities solvents, enabling their solution dispersibility processability─properties not readily available case well-established, insoluble, frameworks. Here, we present critical review summarizing detail recent progress breakthroughs─especially during past five years─of while taking close look at strategic design, precise synthesis, including both irreversible bond-forming chemistry dynamic chemistry, advanced characterization, diverse applications. We highlight representative POC examples an attempt gain some understanding structure–function relationships. also discuss future challenges opportunities application POCs. anticipate this will be useful researchers working field when it comes designing developing desired functions.

Язык: Английский

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From Supramolecular Organic Cages to Porous Covalent Organic Frameworks for Enhancing Iodine Adsorption Capability by Fully Exposed Nitrogen‐Rich Sites

Small, Год журнала: 2023, Номер 19(34)

Опубликована: Май 10, 2023

In order to overcome the limitations of supramolecular organic cages for their incomplete accessibility active sites in solid state and uneasy recyclability liquid solution, herein a nitrogen-rich cage is rationally linked into framework systems four isoreticular covalent frameworks (COFs), that is, Cage-TFB-COF, Cage-NTBA-COF, Cage-TFPB-COF, Cage-TFPT-COF, are successfully synthesized. Structure determination reveals they all high-quality crystalline materials derived from eclipsed packing related two-dimensional frameworks. Since usually have high affinity toward iodine species, adsorption investigations carried out results show them display an enhancement capacities. Especially, Cage-NTBA-COF exhibits capacity 304 wt%, 14-fold higher than sample packed itself. The strong interactions between adsorbed species revealed by spectral analyses. This work demonstrates that, utilizing reticular chemistry strategy extend close-packed porous solids, inherent properties can be greatly exploited targeted applications.

Язык: Английский

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Picking the lock of coordination cage catalysis

Chemical Science, Год журнала: 2023, Номер 14(41), С. 11300 - 11331

Опубликована: Янв. 1, 2023

We provide an overview of coordination cage catalysis, highlighting how mechanistic understanding can help address the challenges in this area leading to new opportunities non-covalent reactivity.

Язык: Английский

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Polycage membranes for precise molecular separation and catalysis

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Май 30, 2023

The evolution of the chemical and pharmaceutical industry requires effective less energy-intensive separation technologies. Engineering smart materials at a large scale with tunable properties for molecular is challenging step to materialize this goal. Herein, we report thin film composite membranes prepared by interfacial polymerization porous organic cages (POCs) (RCC3 tren cages). Ultrathin crosslinked polycage selective layers (thickness as low 9.5 nm) are obtained high permeance strict sieving nanofiltration. A dual function achieved combining catalysis. This demonstrated impregnating highly catalytically active Pd nanoclusters ( ~ 0.7 nm). While membrane promotes precise separation, its catalytic activity enables surface self-cleaning, reacting any potentially adsorbed dye recovering original performance. strategy opens opportunities development other different functions well-tailored abilities.

Язык: Английский

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Metal-N-Heterocyclic Carbene Chemistry Directed toward Metallosupramolecular Synthesis and Beyond

Accounts of Chemical Research, Год журнала: 2023, Номер 56(10), С. 1213 - 1227

Опубликована: Апрель 26, 2023

ConspectusAs versatile, modular, and strongly coordinating moieties in organometallic compounds, N-heterocyclic carbenes (NHCs) have led to numerous breakthroughs transition-metal catalysis, main group chemistry, organocatalysis. In contrast, the chemistry of NHC-based metallosupramolecular assemblies, which discrete individual components are held together via metal (M)–CNHC bonds, has been underdeveloped. Integrating NHCs into supramolecular assemblies would endow them with some unforeseen functions. However, one most critical challenges is seeking an appropriate combination rigid CNHC–M–CNHC units resulting topologies applications. Toward this goal, for last decade we focused on development M–NHC directed toward synthesis. This Account aims summarize our contributions application synthesis from structural design postassembly modification (PAM) their functional applications since integrating garnered much attention among organometallic, photochemical, researchers. While presenting representative examples architectures, try illustrate purposes concepts behind systems developed aid rational approach fabrication complex M–NHC-templated photochemical reactions.We present synthetic approaches new architectures by starting NHC precursors, including poly-NHC-based mechanically interlocked metallacages heteroleptic based electronic complementary self-sorting mechanisms. The regulation increasing topological complexity elaborated selective combinations tetraphenylethylene (TPE) units, backbones, N-wingtip substituents a controllable manner.Subsequently, move elucidating PAM that leads organic cages featuring polyimidazolium/triazolium groups different shapes sizes difficult access using alternative approaches. These possess well-defined cavities, situ-generated sites ideal platforms stabilizing nanoparticles (MNPs) within cavities improved catalytic performance.Finally, demonstrate how templates synthesize cyclobutane derivatives homogeneous solutions fashion. Selected template-dependent transformations photoreactions discussed. Their molecular recognition, aggregation-induced emission (AIE), cell imaging, anticancer activity, radical stimuli-responsive materials also described.Taken together, proven be powerful methods constructing diverse methodology still its infancy, tremendous growth potential promising future. We believe will guide researchers fascinating valuable M–carbene species

Язык: Английский

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A charge-neutral organic cage selectively binds strongly hydrated sulfate anions in water

Nature Chemistry, Год журнала: 2024, Номер 16(3), С. 335 - 342

Опубликована: Фев. 13, 2024

Язык: Английский

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Bioactive compound encapsulation: Characteristics, applications in food systems, and implications for human health

Food Chemistry X, Год журнала: 2024, Номер 24, С. 101953 - 101953

Опубликована: Ноя. 2, 2024

Nanotechnology plays a pivotal role in food science, particularly the nanoencapsulation of bioactive compounds, to enhance their stability, bioavailability, and therapeutic potential. This review aims provide comprehensive analysis encapsulation emphasizing characteristics, applications, implications for human health. work offers detailed comparison polymers such as sodium alginate, gum Arabic, chitosan, cellulose, pectin, shellac, xanthan gum, while also examining both conventional emerging techniques, including freeze-drying, spray-drying, extrusion, coacervation, supercritical anti-solvent drying. The contribution this lies highlighting improving system controlling release rates, maintaining bioactivity under extreme conditions, reducing lipid oxidation. Furthermore, it explores recent technological advances aimed at optimizing processes targeted therapies functional foods. findings underline significant potential not only supplements foods but supportive medical treatments, showcasing its relevance health various contexts.

Язык: Английский

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Explainable chemical artificial intelligence from accurate machine learning of real-space chemical descriptors

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 21, 2024

Abstract Machine-learned computational chemistry has led to a paradoxical situation in which molecular properties can be accurately predicted, but they are difficult interpret. Explainable AI (XAI) tools used analyze complex models, highly dependent on the technique and origin of reference data. Alternatively, interpretable real-space employed directly, often expensive compute. To address this dilemma between explainability accuracy, we developed SchNet4AIM, SchNet-based architecture capable dealing with local one-body (atomic) two-body (interatomic) descriptors. The performance SchNet4AIM is tested by predicting wide collection quantities ranging from atomic charges delocalization indices pairwise interaction energies. accuracy speed breaks bottleneck that prevented use chemical descriptors systems. We show group indices, arising our physically rigorous atomistic predictions, provide reliable indicators supramolecular binding events, thus contributing development Chemical Artificial Intelligence (XCAI) models.

Язык: Английский

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Computationally guided synthesis of a hierarchical [4[2+3]+6] porous organic ‘cage of cages’

Nature Synthesis, Год журнала: 2024, Номер 3(7), С. 825 - 834

Опубликована: Апрель 26, 2024

Abstract Here we report a two-step, hierarchical synthesis that assembles trigonal prismatic organic cage into more symmetric, higher-order tetrahedral cage, or ‘cage of cages’. Both the preformed [2+3] building blocks and resultant [4[2+3]+6]cage molecule are constructed using ether bridges. This strategy affords excellent hydrolytic stability is not feature common dynamic linkers, such as imines. Despite its relatively high molar mass (3,001 g mol −1 ), exhibits good solubility crystallizes porous superstructure with surface area 1,056 m 2 . By contrast, block porous. The shows CO SF 6 uptakes due to polar skeleton. preference for over other products can be predicted by computational modelling, crystal packing, suggesting broader design assembly cages synthetically engineered functions.

Язык: Английский

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Phenol[4]arenes: Excellent Macrocyclic Precursors for Constructing Chiral Porous Organic Cages

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 2, 2025

The development of new chiral building blocks for constructing complex architectures, such as macrocycles and cages, is both crucial challenging. Although concave-shaped calixarenes have been established versatile the synthesis cage compounds, there are no reports on cages constructed from calix[4]arene derivatives. Herein, we present a straightforward effective method gram-scale member macrocycle enantiomers, namely, phenol[4]arene (PC[4]A). As proof concept, functionalized these enantiomers into tetraformylphenol[4]arene (PC[4]ACHO) derivatives via Duff reaction to construct porous organic (CPOCs) using polyamine synthons. Specifically, employ two fluorescent amine synthons, bis(4-aminophenyl)phenylamine tris(4-aminophenyl)amine, assemble with PC[4]ACHO resulting in [2 + 4] lantern-shaped [6 8] truncated octahedral CPOCs, respectively. These structures unambiguously characterized by single-crystal X-ray diffraction circular dichroism (CD) spectroscopy. Notably, CPOCs exhibit internal diameters approximately 3.1 nm, cavity volume around 5300 Å3, high specific surface areas up 1300 m2 g-1 after desolvation, making them among largest reported. Additionally, investigations their sensing performance demonstrate that PC[4]A-based enable enantioselective recognition amino acids This work strongly suggests PC[4]A can serve an excellent block rational design materials practical applications.

Язык: Английский

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