A porous metal-organic cage liquid for sustainable CO2 conversion reactions

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

Опубликована: Июнь 7, 2023

Porous liquids are fluids with the permanent porosity, which can overcome poor gas solubility limitations of conventional porous solid materials for three phase gas-liquid-solid reactions. However, preparation still requires complicated and tedious use hosts bulky liquids. Herein, we develop a facile method to produce metal-organic cage (MOC) liquid (Im-PL-Cage) by self-assembly long polyethylene glycol (PEG)-imidazolium chain functional linkers, calixarene molecules Zn ions. The Im-PL-Cage in neat has porosity fluidity, endowing it high capacity CO2 adsorption. Thus, stored an be efficiently converted value-added formylation product atmosphere, far exceeds MOC nonporous PEG-imidazolium counterparts. This work offers new prepare catalytic transformation adsorbed molecules.

Язык: Английский

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Molecular Barrels as Potential Hosts: From Synthesis to Applications

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(14), С. 7692 - 7711

Опубликована: Март 28, 2023

Self-assembled discrete molecular architectures that show selective recognition within their internal cavities are highly desirable. Such hosts often guest through several noncovalent interactions. This emulates the activity of naturally occurring enzymes and proteins. Research in formation 3D cages different shapes sizes has progressed rapidly since development coordination-driven self-assembly dynamic covalent chemistry. find applications catalysis, stabilization metastable molecules, purification isomeric mixtures via encapsulation, even biomedical applications. Most these stem from ability host to bind guests strongly a fashion, providing suitable environment for perform functions. Molecular having closed with small windows either poor encapsulation or inhibit easy release while those wide open structures fail form stable host-guest complexes. In this context, barrels obtained by metal-ligand/covalent bond techniques possess optimized architectures. With hollow-walled cavity two large openings, satisfy structural requirements many perspective, we will discuss detail synthetic strategies obtaining barrel-like employing coordination interactions, structure-based classification, storing transient separation chemicals, photoinduced antibacterial activity. We aim highlight advantages over other efficiently carrying out functions new

Язык: Английский

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Potential of nonporous adaptive crystals for hydrocarbon separation

Chemical Society Reviews, Год журнала: 2023, Номер 52(17), С. 6075 - 6119

Опубликована: Янв. 1, 2023

The adsorptive separation based on nonporous adaptive crystals (NACs) is an attractive green technology. Herein, we comprehensively summarize recent advances in various supramolecular hosts-based NACs for hydrocarbon separation.

Язык: Английский

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Enhanced Activity of Enzyme Immobilized on Hydrophobic ZIF‐8 Modified by Ni²⁺ Ions

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(7)

Опубликована: Дек. 20, 2022

The development of efficient enzyme immobilization to promote their recyclability and activity is highly desirable. Zeolitic imidazolate framework-8 (ZIF-8) has been proved be an effective platform for due its easy preparation biocompatibility. However, the intrinsic hydrophobic characteristic hinders further in this filed. Herein, a facile synthesis approach was developed immobilize pepsin (PEP) on ZIF-8 carrier by using Ni2+ ions as anchor (ZIF-8@PEP-Ni). By contrast, direct coating PEP surface (ZIF-8@PEP) generated significant conformational changes. Electrochemical oxygen evolution reaction (OER) employed study catalytic immobilized PEP. ZIF-8@PEP-Ni composite attains remarkable OER performance with ultralow overpotential only 127 mV at 10 mA cm-2 , which much lower than 690 919 values ZIF-8@PEP PEP, respectively.

Язык: Английский

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Trefoil-Shaped Metal–Organic Cages as Fluorescent Chemosensors for Multiple Detection of Fe³⁺, Cr₂O₇^2–, and Antibiotics

Inorganic Chemistry, Год журнала: 2023, Номер 62(4), С. 1297 - 1305

Опубликована: Янв. 17, 2023

The construction of metal-organic cages (MOCs) with specific structures and fluorescence sensing properties is much importance challenging. Herein, a novel phenanthroline-based cage, [Cd3L3·6MeOH·6H2O] (1), was synthesized by metal-directed assembly the ligand 3,3'-[(1E,1'E)-(1,10-phenanthroline-2,9-diyl)bis(ethene-2,1-diyl)]dibenzoic acid (H2L) CdI2 using solvothermal method. According to single-crystal X-ray analysis, cage 1 exhibits rare trefoil-shaped structure. Meanwhile, discrete MOCs are further stacked into 3D porous supramolecular structure through abundant intermolecular C-H···O interactions. Additionally, exploration on cations, anions, antibiotics in aqueous solution, experimental results indicate that has excellent abilities for Fe3+, Cr2O72-, nitrofuran nitroimidazole antibiotics. ability remains unaltered five cycles toward all analytes. above suggested can be considered potential multiple sensor detection some

Язык: Английский

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Construction and Hierarchical Self-Assembly of Multifunctional Coordination Cages with Triangular Metal–Metal-Bonded Units

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(13), С. 7446 - 7453

Опубликована: Март 22, 2023

Herein, a series of face-capped (Tr2M3)4L4 (Tr = cycloheptatrienyl cationic ring; M metal; L organosulfur ligand) tetrahedral cages 1-3 functionalized with 12 appended crown ether moieties were designed and synthesized. The reversible binding ammonium cations peripheral to adjust internal guest-binding was realized. Combination bisammonium linker cage 3 led the formation supramolecular gel SPN1 via host-guest interactions between salts. obtained exhibited multiple-stimuli responsiveness, injectability, excellent self-healing properties could be further developed SPN1-based drug delivery system. In addition, storage modulus 20 times higher than that model without Pd-Pd bonded blocks, had better compared latter, demonstrating importance such in improving mechanical strength losing dynamic material. cytotoxicity vitro drug-loaded (doxorubicin or methotrexate) significantly improved free drugs.

Язык: Английский

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Self-Assembly and Photothermal Conversion of MetallaRussian Doll and Metalla[2]catenanes Induced via Multiple Stacking Interactions

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(32), С. 18036 - 18047

Опубликована: Июль 17, 2023

A variety of organometallic supramolecular architectures have been constructed over the past decades and their properties were also explored via different strategies. However, synthesis metalla-Russian doll is still a fascinating challenge. Herein, series new coordination complexes, including doll, metalla[2]catenanes, metallarectangles, synthesized by using meticulously selected Cp*Rh (Cp* = η5-C5Me5) building units (E1, E2, E3) three rigid anthracylpyridine ligands (L1, L2, L3) self-assembly strategy. While combination short ligand L1 E1 or E2 generated two longer L2 containing an alkynyl group resulted in [2]catenanes, most likely due to which strong electron-donating effect groups causes self-accumulation. Interestingly, unusual Russian assembly was obtained through reaction L3 E3 based on sextuple π···π stacking interactions. Furthermore, dynamic structural conversion between [2]catenanes corresponding metallarectangles could be observed concentration-, solvent-, guest-induced effects. The [2]catenane complexes 4b displayed efficient photothermal efficiency solution (20.2%), comparison with other macrocycles. We believe that interactions generate active nonradiative pathways promote radiative photodeactivation pathways. This study proves versatility half-sandwich units, not only build complicated topologies but effective functional materials for various appealing applications.

Язык: Английский

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A B←N framework based on 1D dative B←N polymers for exclusive recognition and separation of benzene from its azeotrope

Chem, Год журнала: 2023, Номер 9(12), С. 3532 - 3543

Опубликована: Авг. 22, 2023

Язык: Английский

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A Cu^I₆L₄ Cage Dynamically Reconfigures to Form Suit[4]anes and Selectively Bind Fluorinated Steroids

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(15), С. 10234 - 10239

Опубликована: Апрель 5, 2024

Simple organic ligands can self-assemble with metal ions to generate metal–organic cages, whose cavities bind guests selectively. This binding may enable new methods of chemical separation or sensing, among other useful functions. Here we report the preparation a CuI6L4 pseudo-octahedral cage, which from simple building blocks. Temperature, solvent, and presence different governed structure predominated dynamic mixture cage diastereomers arrangements right- left-handed vertices. Dissolution in dimethyl sulfoxide tetrahedral led chiral T-symmetric framework, whereas low temperatures favored achiral S4-symmetric diastereomer. Tetrahedral long arms were encapsulated form mechanically bonded suit[4]anes, guest protruding out through host windows. The was also observed fluorinated steroids, an important class drug molecules, but not non-fluorinated providing basis for processes.

Язык: Английский

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54 K Spin Transition Temperature Shift in a Fe₆L₄ Octahedral Cage Induced by Optimal Fitted Multiple Guests

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(11), С. 7811 - 7821

Опубликована: Март 7, 2024

Spin-crossover (SCO) coordination cages are at the forefront of research for their potential in crafting next-generation molecular devices. However, due to scarcity SCO hosts and own limited cavities, interplay between host multiple guests binding has remained elusive. In this contribution, we present a family pseudo-octahedral (M6L4, M = ZnII, CoII, FeII, NiII) assembled from tritopic tridentate ligand L with metal ions. The utilization FeII ion leads successful creation Fe6L4-type cage. Host–guest studies these M6L4 reveal capacity encapsulate four adamantine-based guests. Notably, spin transition temperature T1/2 Fe6L4 is dependent on encapsulated. inclusion adamantine yields an unprecedented shift 54 K, record guest-mediated date. This drastic ascribed synergistic effect coupled optimal fit within host. Through straightforward thermodynamic cycle, affinities high-spin (HS) low-spin (LS) states separated apparent constant. result indicates that LS state stronger affinity than HS state. Exploring thermodynamics host–guest complexes allows us examine cavity. study reveals can be manipulated by encapsulation guests, cage ideal candidate determining guest fit.

Язык: Английский

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