N-Heterocyclic Carbene-Stabilized Gold Nanoclusters with Organometallic Motifs for Promoting Catalysis

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(24), P. 10844 - 10853

Published: June 7, 2022

The complexity of heterogeneous metal catalysts makes it challenging to gain insights into their catalytic mechanisms. Thus, there exists a huge gap between catalysis and organometallic catalysis. With the success in preparation highly robust atomically precise nanocluster (i.e., [Au16(NHC-1)5(PA)3Br2]3+ [Au17(NHC-1)4(PA)4Br4]+, where NHC-1 is bidentate NHC ligand, PA phenylacetylide) with surface motifs anchored on metallic core, we demonstrate this work how core works synergistically enhance More importantly, discovery allows development stable recyclable achieve efficient hydroamination alkynes an extremely low catalyst dosage (0.002 mol %), helping bridge homogeneous modification nanocatalysts provides new design principle enhanced

Language: Английский

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Porous organic polycarbene nanotrap for efficient and selective gold stripping from electronic waste

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Jan. 17, 2023

Abstract The role of N-heterocyclic carbene, a well-known reactive site, in chemical catalysis has long been studied. However, its unique binding and electron-donating properties have barely explored other research areas, such as metal capture. Herein, we report the design preparation poly(ionic liquid)-derived porous organic polycarbene adsorbent with superior gold-capturing capability. With carbene sites network “nanotrap”, it exhibits an ultrahigh gold recovery capacity 2.09 g/g. In-depth exploration complex ion environment electronic waste-extraction solution indicates that possesses significant efficiency 99.8%. X-ray photoelectron spectroscopy along nuclear magnetic resonance reveals high performance results from formation robust metal-carbene bonds plus ability to reduce nearby ions into nanoparticles. Density functional theory calculations indicate energetically favourable multinuclear Au enhances adsorption clusters. Life cycle assessment cost analysis synthesis adsorbents potential for application industrial-scale productions. These reveal apply chemistry materials science highlight promising new material precious recovery.

Language: 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, Journal Year: 2023, Volume and Issue: 19(34)

Published: May 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.

Language: Английский

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Carbene-stabilized enantiopure heterometallic clusters featuring EQE of 20.8% in circularly-polarized OLED

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: July 11, 2023

Bright and efficient chiral coinage metal clusters show promise for use in emerging circularly polarized light-emitting materials diodes. To date, highly organic diodes (CP-OLEDs) with enantiopure have not been reported. Herein, through rational design of a multidentate N-heterocyclic carbene (NHC) ligand modular building strategy, we synthesize series Au(I)-Cu(I) exceptional stability. Modulation the ligands stabilize excited states to allow thermally activated delayed fluorescence, resulting highest orange-red photoluminescence quantum yields over 93.0% solid state, which is accompanied by luminescence. Based on solution process, prototypical CP-OLED considerably high external efficiency 20.8% prepared. These results demonstrate extensive designability NHC polymetallic performance chiroptical applications.

Language: Английский

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Molecular Co-Catalyst Confined within a Metallacage for Enhanced Photocatalytic CO₂ Reduction

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(3), P. 2275 - 2285

Published: Jan. 12, 2024

The construction of structurally well-defined supramolecular hosts to accommodate catalytically active species within a cavity is promising way address catalyst deactivation. resulting catalysts can significantly improve the utilization catalytic sites, thereby achieving highly efficient chemical conversion. In this study, Co-metalated phthalocyanine (

Language: Английский

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Porous covalent organic framework liquid for boosting CO2 adsorption and catalysis via dynamically expanding effect

National Science Review, Journal Year: 2025, Volume and Issue: 12(3)

Published: Jan. 24, 2025

ABSTRACT The features of intrinsic porosity and fluidity endow porous liquids (PLs) with unique properties performance but the preparation PLs remains challenging due to difficulty in liquefying keeping at same time. Herein, we develop a stepwise surface functionalization ion exchange strategy achieve rare example flexible covalent organic framework (COF)-based PL (COF-PLs). By coating outer judiciously selected three-dimensional COF-301 an imidazolium salt corona, followed by liquefaction using anion canopy potassium poly(ethylene glycol) sulfonate (PEGS) via electrostatic interactions, PL, COF-301-PL, can be obtained. Theoretical calculations CO2 adsorption experiments reveal that cavities COF-301-PL undergo dynamic adjustments response changes pressure. expansion effect not only provide additional gas capacity (7.04 mmol/g 40 bar) also facilitate mass transfer molecules during catalytic process. Consequently, exhibits superior efficiency for conversion into cyclic carbonate factor 24 17 compared those PEGS solid counterpart, respectively. optimization substrate conditions consequently improves overall reactions. This work offers new perspective on their great potential application catalysis.

Language: Английский

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A CO₂‐Masked Carbene Functionalized Covalent Organic Framework for Highly Efficient Carbon Dioxide Conversion

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(40)

Published: July 5, 2022

Free N-heterocyclic carbenes (NHCs) are generally prepared by treatment of imidazolium precursors with strong alkali reagents, which usually produces inactive NHC dimers. This would destroy porous supports and thus make supported catalysts difficult to recovery reuse. Herein, we report the first stable CO2 -masked grafted on a crystalline covalent organic framework (COF). The NHC-CO2 moieties in COF-NHC-CO2 could be transformed situ into isolated NHCs heating, exhibit superior catalytic performances hydrosilylation N-formylation reactions . sites can reversibly form easily recycled reused while maintaining excellent activity. Density functional theory calculations revealed that fully exposed after removal -masks rapidly react silanes, endows COF-NHC high

Language: Английский

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A General Base-free Route toward the Building of Metal N-Heterocyclic Carbenes into Covalent Organic Frameworks for CO₂ Conversion

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 3943 - 3954

Published: Feb. 27, 2024

Covalent organic frameworks (COFs) would be a promising platform to immobilize metal N-heterocyclic carbenes (M-NHCs) for efficient CO2 conversion, but they are seldom reported. Herein, we develop facile base-free strategy prepare M-NHCs (M = Ir, Au, Pd) decorated M-NHC–COFs (Ir-NHC–COF, Au-NHC–COF, and Pd-NHC–COF) via the reactions of imidazolium carboxylate functionalized NHC-based COF (NHC–CO2–COF) with corresponding complexes under mild conditions. This synthesis method generation desired M-NHC single sites avoids handling free use strong bases. The obtained Ir-NHC–COF catalyst showed catalytic activity recyclability in hydrogenation process, attaining noteworthy turnover frequency up 17244 h–1, which placed it among top-performing heterogeneous catalysts this reaction. study presents universal straightforward approach attaching functional onto COFs, offering combined advantages acting as highly reactions. general widely applicable other M-NHC-functionalized porous materials covalently bound various applications future.

Language: Английский

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1H-1,2,3-Triazol-5-ylidenes as Catalytic Organic Single-Electron Reductants

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 2933 - 2938

Published: Jan. 22, 2024

Most of the known single-electron reductants are either metal based reagents, used in a stoichiometric amount, or combination an organic species and photocatalyst. Here we report that 1

Language: Английский

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Synthesis of Carborane-Backbone Metallacycles for Highly Selective Capture ofn-Pentane

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(48), P. 22221 - 22228

Published: Nov. 28, 2022

The specific recognition and separation of alkanes with similar molecular structures close boiling points face significant scientific challenges industrial demands. Here, rectangular carborane-based metallacycles were designed to selectively encapsulate n-pentane from n-pentane, iso-pentane, cyclo-pentane mixtures in a simple-to-operate more energy-efficient way. Metallacycle 1, bearing 1,2-di(4-pyridyl) ethylene, can separate these three-component purity 97%. selectivity is ascribed the capture preferred guest matching size, C-H···π interactions, potential B-Hδ-···Hδ+-C interactions. Besides, removal gives rise original guest-free metallacycles, which be recycled without losing performance. Considering variety substituted carborane derivatives, metal ions, organic linkers, new supramolecular coordination complexes (SCCs) may broadly applicable other challenging systems good

Language: Английский

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