Metal–organic cages for gas adsorption and separation

Chemical Communications, Год журнала: 2024, Номер 60(26), С. 3469 - 3483

Опубликована: Янв. 1, 2024

In this highlight, we summarize the design principle and representative examples of MOCs for gas adsorption separation, with aim providing a theoretical basis designing more that can adsorb purify gas.

Язык: Английский

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Host–Guest Interactions Induced Enhancement in Oxidase-Like Activity of a Benzothiadiazole Dye Inside an Aqueous Pd₈L₄ Barrel

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(36), С. 24901 - 24910

Опубликована: Авг. 28, 2024

The effect of host–guest interactions on the chemistry encapsulated molecules is a fascinating field research that has gained momentum in recent years. Much work this been focused such catalysis and photoluminescence dyes. However, related photoinduced processes, as photoregulated oxidase-mimicking activity, not explored much. Herein, we report unique example enhancement oxidase-like activity benzothiadiazole dye (G1) water through encapsulation within M8L4 molecular barrel (1). Favorable helped guest G1 to have better electron transfer oxygen leading increased production superoxide radical anions activity. Furthermore, inside 1 also caused change redox potentials which after produced oxidizing agent than free G1. These phenomena combined enhance upon cage 1. present demonstrates processes.

Язык: Английский

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Uncovering tetrazoles as building blocks for constructing discrete and polymeric assemblies

Chemical Communications, Год журнала: 2024, Номер 60(43), С. 5573 - 5585

Опубликована: Янв. 1, 2024

Metal-organic self-assembly with flexible moieties is a budding field of research due to the possibility formation unique architectures. Tetrazole, characterised by four nitrogen atoms in five-member ring, exhibits immense potential as component. Tetrazole offers coordination sites for binding metal centre nine distinct modes, leading various assemblies. This review highlights different polymeric and discrete tetrazole-based assemblies their functions. The meticulous manipulation stoichiometry, ligands, ions required constructing has also been discussed. applications these architectures separation, catalysis detection have accentuated. latter section consolidates cage composites, highlighting cell imaging photocatalytic applications.

Язык: Английский

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Mechanically Interlocked Water-Soluble Pd₆ Host for the Selective Separation of Coal Tar-Based Planar Aromatic Molecules

Inorganic Chemistry, Год журнала: 2024, Номер 63(32), С. 14924 - 14932

Опубликована: Июнь 19, 2024

Research on the synthesis of catenated cages has been a growing field interest in past few years. While multiple types with different structures have synthesized, application such systems much less explored. Specifically, use separation industrially relevant molecules that are present coal tar not explored before. Herein, we demonstrate newly synthesized interlocked cage 1 [C184H240N76O48Pd6] (M6L4), formed through self-assembly ligand L.HNO3 (tris(4-(1H-imidazole-1-yl)benzylidene)hydrazine-1-carbohydrazonhydrazide) acceptor cis-[(tmchda)Pd(NO3)2] [tmchda = ±N,N,N′,N′-tetramethylcyclohexane-1,2-diamine] (M). The was able to separate isomers (anthracene and phenanthrene) using simple solvent extraction technique. Using same technique, more difficult structurally physiochemically similar compounds acenaphthene acenaphthylene performed for first time as host. Other noninterlocked hexanuclear Pd6 having wider cavity proved inefficient separation, demonstrating uniqueness challenging separation.

Язык: Английский

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Stimuli‐Mediated Structural Interchange Between Pd6 and Pd12 Architectures: Selective Recognition of E‐Stilbene by the Pd6 Architecture and its Photoprotection

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(50)

Опубликована: Авг. 20, 2024

Abstract The dynamic behaviour of metal‐ligand bonding cultivates stimuli‐mediated structural transformations in self‐assembled molecular architectures. propensity synthetically designed systems to interchange between higher‐order architectures is increased multi‐fold when the building blocks have higher conformational degrees freedom. Herein, we report a new ligand, (2,7‐bis(di(pyridin‐4‐yl)amino)‐9 H ‐fluoren‐9‐one) ( L ), which, upon self‐assembly with cis ‐[(ethylene‐1,2‐diamine)Pd(NO 3 ) 2 ] acceptor M resulted formation 6 trifacial barrel C1 water. Interestingly, during crystallization, rare 12 triangular orthobicupola architecture C2 was generated along . could also be solution via application several stimuli. aqueous media stabilize one trans ‐stilbene tS or cS molecule its cavity, selectivity for former from their mixture. Moreover, acted as an effective host prevent otherwise facile photoisomerization inside hydrophobic cavity under UV irradiation. Conversely, visible‐light‐induced reverse isomerization encapsulated achieved readily due better stabilization within and transparency visible light. A multi‐functional system therefore designed, which at same time stimuli‐responsive, shows isomer selectivity, photo‐protects ‐stilbene.

Язык: Английский

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Revisiting the Origins of Reactivity and Selectivity in the Pd₆L₄-Cage-Catalyzed Diels–Alder Reactions: A Combined Computational and Experimental Study

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

Supramolecular metal–organic cages (MOCs) have gained attention as versatile catalytic platforms due to their self-assembled architectures and well-defined cavities, which mimic enzyme active sites enable spatial confinement. This confinement modulates the reaction pathways enhances performance. Recent studies highlight potential in various organic transformations, but factors governing MOC-catalyzed reactions remain incompletely understood. work builds on prior computational of Diels–Alder catalyzed by palladium-based MOCs, showing that common view transition-state stabilization via π–π interactions is not valid. Instead, we find between substrate ligands destabilize transition state. Additionally, theoretical regioselectivity, validated experimentally, suggest encapsulation efficiency key determining selectivity. These findings provide new insights into mechanisms reactions.

Язык: Английский

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Chemo-Selective Transformation of Anthracene Derivative within Water-Soluble Coordination Cages Having Different Cavities

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 12, 2025

Coordination cages with specific properties and functionalities are utilized as reaction vessels for the desired chemical transformation of substrates. The symmetry inherent cavity coordination can influence host–guest interactions outcome in their confined space. However, impact cage shape on different transformations remains unclear. In this chapter, we report chemo-selective anthracene derivative using three geometrically distinct Pd6 (CC2, CC3, CC4). Photoirradiation 9-bromoanthracene (G3) distorted double-square (CC2) yields anthracene-9,10-dione, while known (CC3) forms a [4 + 4] cycloaddition product. same bowl-shaped (CC4) resulted oxidized Through combination experimental computational studies, demonstrate that size significantly pathways encapsulated derivative, leading to chemo-selectivity. Furthermore, observe encapsulation cavities (CC2 CC4) leads significant enhancement rate photooxidation G3. This work underscores versatility water-soluble synthetic chemistry, offering interesting avenues transformation.

Язык: Английский

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Formation of a Pd₁₆ Molecular Basket Architecture of Reduced Symmetry and Angular Deviation in a Fluorenone Scaffold to Govern the Host–Guest Chemistry of Pd₆ Trifacial Tubes

JACS Au, Год журнала: 2025, Номер 5(5), С. 2368 - 2378

Опубликована: Май 9, 2025

The employment of flexible ligands with significant conformational freedom in coordination-driven self-assembly enables the formation unique and intricate structures. In this study, such a fluorenone-appended ligand (L1) sterically demanding acceptor, [Pd-(tmed)-(ONO2)2] (M1), generated new molecular basket architecture, (M1) 16 8 (B), featuring large hollow cavity. B possesses an unusual twisted architecture low symmetry, consisting Pd-(II) centers arranged as four tetrahedra connected by eight ligands, representing structurally complex system reminiscent biological architectures. Designing entropically disfavored, architectures reduced symmetry is challenging but desirable, since they can act ideal models to study complicated natural systems. host-guest property supramolecular hosts governed confined cavities noncovalent interactions, which are dictated angular disposition coordination sites. To explore this, fluorenone scaffold was used synthesize two other tetradentate (L2 L3) that differed spatial distributions their vectors. these [Pd-(en)-(ONO2)2] (M2) resulted water-soluble 6 (L1/L2/L3) 3 trifacial tubes different geometries varying internal cavity dimensions. These variations further altered orientation carbonyl groups within cavities, thereby modulating guest binding abilities highlighting importance tailoring for specific binding.

Язык: Английский

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Dual Capture of Iodine and Methyl Iodide Using Nonporous Nitrogen-Enriched Palladium(II) Assemblies

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Июнь 3, 2025

The increasing reliance on nuclear energy amid fossil fuel depletion has intensified the demand for effective materials to capture and store radioactive species. Among these, molecular iodine methyl iodide present serious environmental health risks due their volatility persistence in waste. Herein, four nonporous self-assembled metallo-supramolecular assemblies (C1-C4) containing nitrogen-enriched cores (pyridyl, pyrimidine, or phenazine units) with distinct cavity sizes were investigated potential simultaneous of both organic iodide. In vapor phase, achieved exceptional uptake up 3.03 g g-1 at 75 °C, n-hexane solution, capacities reached 493.5 mg g-1, highlighting materials' efficiency across different phases facilitated by electron-pair interactions. Additionally, these exhibited excellent performance capturing vapor, adsorption as high 1.2 via methylation reactions. proved be robust reusable, maintaining efficacy over least five cycles without significant degradation. This work presents first report an N-heteroatom functionalization approach design recyclable coordination safe efficient storage iodide, contributing mitigation energy-associated risks.

Язык: Английский

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Effective separation of phenanthrene from isomeric anthracene using a water-soluble macrocycle-based cage

Chinese Chemical Letters, Год журнала: 2024, Номер unknown, С. 110164 - 110164

Опубликована: Июнь 1, 2024

Язык: Английский

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