Chemical Flexibility of Atomically Precise Metal Clusters

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(11), P. 7262 - 7378

Published: May 2, 2024

Ligand-protected metal clusters possess hybrid properties that seamlessly combine an inorganic core with organic ligand shell, imparting them exceptional chemical flexibility and unlocking remarkable application potential in diverse fields. Leveraging to expand the library of available materials stimulate development new functionalities is becoming increasingly pressing requirement. This Review focuses on origin from structural analysis, including intra-cluster bonding, inter-cluster interactions, cluster-environments metal-to-ligand ratios, thermodynamic effects. In introduction, we briefly outline explain differences commonalities M(I)/M(I/0) coinage clusters. Additionally, distinguish bonding characteristics atoms core, which give rise their distinct flexibility. Section 2 delves into categories, theories related following sections 3 7, primarily elucidate mechanisms trigger flexibility, dynamic processes transformation, resultant alterations structure, ensuing modifications physical–chemical properties. 8 presents notable applications have emerged utilizing assemblies. Finally, section 9, discuss future challenges opportunities within this area.

Language: Английский

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Progress and prospects in the design of functional atomically-precise Ag(I)-thiolate nanoclusters and their assembly approaches

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 492, P. 215255 - 215255

Published: June 6, 2023

Language: Английский

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Atomically Precise Silver Clusters Stabilized by Lacunary Polyoxometalates with Photocatalytic CO₂ Reduction Activity

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(7)

Published: Dec. 28, 2023

Abstract The syntheses of atomically precise silver (Ag) clusters stabilized by multidentate lacunary polyoxometalate (POM) ligands have been emerging as a promising but challenging research direction, the combination redox‐active POM and will render them unexpected geometric structures catalytic properties. Herein, we report successful construction two structurally‐new POM‐stabilized Ag clusters, TBA 6 H 14 (DPPB) 4 (CH 3 CN) 9 [Ag 24 (Si 2 W 18 O 66 ) ] ⋅ 10CH CN 9H ( {Ag } , TBA=tetra‐ n ‐butylammonium, DPPB=1,4‐Bis(diphenylphosphino)butane) Na (H O) 27 8CH 10H ), using facile one‐pot solvothermal approach. Under otherwise identical synthetic conditions, molecular could be readily tuned addition different organic ligands. In both compounds, central trefoil‐propeller‐shaped 14+ 17+ bearing 10 delocalized valence electrons are three C‐shaped {Si units. femtosecond/nanosecond transient absorption spectroscopy revealed rapid charge transfer between core Both compounds pioneeringly investigated catalysts for photocatalytic CO reduction to HCOOH with high selectivity.

Language: Английский

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Two structurally new Lindqvist hexaniobate-templated silver thiolate clusters

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(41), P. 5415 - 5418

Published: Jan. 1, 2024

Two structurally new Lindqvist hexaniobate-templated silver thiolate clusters, [Nb

Language: Английский

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Recent advances in the asymmetrical templation effect of polyoxometalate in silver clusters

Polyoxometalates, Journal Year: 2022, Volume and Issue: 1(2), P. 9140010 - 9140010

Published: Oct. 19, 2022

The design and construction of polyoxometalate (POM)-templated silver clusters have received increasing attention, not only due to their aesthetic structures but also wide applications in chromatic materials, magnetism, electronics, fluorescence. Among various POM-templated clusters, asymmetrically-wrapped POM–silver unusual structures: POMs exposed surfaces an asymmetrically-connected shell, which endows the with distinctive properties, such as redox electrocatalytic activities. This review summarizes recent developments this field, highlighting syntheses, structures, properties clusters. formation mechanisms, challenges, perspectives are discussed. We believe that will motivate development asymmetrical templation effect POM

Language: Английский

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Halide Ion-Templated Atomic Precision Synthesis and Structural Modulation of Silver Sulfide Nanoclusters

Journal of Cluster Science, Journal Year: 2025, Volume and Issue: 36(2)

Published: March 7, 2025

Language: Английский

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The largest aluminum molecular rings: Phenol‐thermal synthesis, photoluminescence, and optical limiting

Aggregate, Journal Year: 2022, Volume and Issue: 4(2)

Published: Aug. 26, 2022

Abstract It is of great interest to modulate the photophysical properties by atomically precise chemical control. The incorporation conjugated ligands into crystalline materials provides a platform for molecular‐level interpretation structure‐activity relationship. Herein, we reported phenol‐thermal and scale‐up synthesis new family remarkably stable aluminum molecular rings. They are assembled twenty Al III ions with large phenols, representing currently largest sizes (up 4 nm in diameter) field main group metal oxo clusters. Phenols not only reaction medium but also auxiliary bridging on surface macrocyclic molecules. In addition, they either parallel center ring or inserted ring, form dimers/tetramers that bind molecules supramolecular structures. These rings hydrophobic ultra‐stable, evidenced retaining their morphology when exposed air more than year. Compared pristine ligands, exhibit coordination‐enhanced fluorescence. By dispersing them polydimethylsiloxane (PDMS) matrix, prepared transparent flexible PDMS thin films coupling display nonlinear optical application. Our discovery such fine‐tuning photo‐related performances.

Language: Английский

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Anion-templated silver nanoclusters: precise synthesis and geometric structure

Science and Technology of Advanced Materials, Journal Year: 2023, Volume and Issue: 24(1)

Published: April 18, 2023

Metal nanoclusters (NCs) are gaining much attention in nanoscale materials research because they exhibit size-specific physicochemical properties that not observed the corresponding bulk metals. Among them, silver (Ag) NCs can be precisely synthesized only as pure Ag but also anion-templated NCs. For NCs, we expect following capabilities: 1) size and shape control by regulating central anion (anion template); 2) stabilization adjusting charge interaction between surrounding atoms; 3) functionalization selecting type of anion. In this review, summarize synthesis methods influences on geometric structure which include halide ions, chalcogenide oxoanions, polyoxometalate, or hydride/deuteride This summary provides a reference for current state may promote development with novel structures properties.

Language: Английский

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Polyoxometalate/poly(3,4-ethylenedioxythiophene) nanocomposites enabling visualization of energy storage status in multicolor electrochromic supercapacitors

Applied Surface Science, Journal Year: 2023, Volume and Issue: 641, P. 158450 - 158450

Published: Sept. 12, 2023

Language: Английский

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Assembly-Induced Emission in Mercaptosuccinic Acid-Templated Silver Nanoclusters: Metal Ion Selectivity and pH Sensitivity

ACS Applied Nano Materials, Journal Year: 2022, Volume and Issue: 5(5), P. 7571 - 7579

Published: May 2, 2022

The phenomenon of aggregation-induced emission (AIE) is an emerging strategy used to tune the optical properties luminescent metal nanoclusters (MNCs). Various external factors such as cations, hydrophobicity, and solvents provide impetus for AIE in MNCs. Our present investigations delineate remarkable tuning photophysical weakly mercaptosuccinic acid (MSA)-templated silver (AgNCs). Upon AgNCs through introduction Zn2+ ions, maximum was shifted from ∼465 ∼670 nm with unusual augmentation photoluminescence intensities (∼3000 times). minimization energy dissipation due formation Zn2+-induced rigid assembly mainly accounts these unprecedented signatures. As a consequence this, otherwise emissive AgNC system (quantum yield, QY ∼ 0.1%) gets converted highly red-emitting (Zn–AgNCs, 2%). MSA-templated demonstrated selectivity toward ions forming Zn–AgNC assemblies, which turn were sensitive pH medium range 5–8.

Language: Английский

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