An Alkynyl‐Stabilized Pt<sub>5</sub>Ag<sub>22</sub> Cluster Featuring a Two‐Dimensional Alkynyl–Platinum “Crucifix Motif”

Shen, Hongliang; Mizuta, Tsutomu

doi:10.1002/chem.201704643

Cited by 18 publications

(15 citation statements)

References 57 publications

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“…In this order, the latter ligands can readily be replaced by the former ligands or removed upon heating or other treatments. Recently, terminal alkynes (RCCH) have been used as a new type of protective ligand of coinage metal nanoclusters/nanoparticles. ,− In this connection, a bimetallic nanocluster containing 44 metal atoms, Au 24 Ag 20 (SPy) 4 (PA) 20 Cl 2 (PA = phenylalkynyl), was successfully prepared and structurally characterized by single-crystal analysis . Three different types of anionic ligands (i.e., PA, SPy, and Cl – ) are present on the cluster surface.…”

Section: Surface Reactivities and Catalytic Activities Of Metal Nanoc...mentioning

confidence: 99%

Surface Chemistry of Atomically Precise Coinage–Metal Nanoclusters: From Structural Control to Surface Reactivity and Catalysis

2018

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CONSPECTUS:A comprehensive understanding of chemical bonding and reactions at the surface of nanomaterials is of great importance in the rational design of their functional properties and applications. With the rapid development in cluster science, it has become clear that atomically precise metal clusters represent ideal models for resolving various important and/or unsolved issues related to surface science. This Account highlights our recent efforts on the fabrication of ligand-stabilized coinage nanoclusters with atomic precision from the viewpoint of surface coordination chemistry in particular. The successful synthesis of a large variety of metal clusters in our group has greatly benefitted from the development of an effective amineassisted NaBH 4 reduction method. First discussed in this Account is how the introduction of amines in the synthetic protocol enhances the long-term stability and high-yield production of Ag/Cu-based metals in air. Such a method allows the utilization of different organic ligands as surface stabilizing agents to manipulate both the core and surface structures of metal nanoclusters, helping to understand the role of surface ligands in determining the structures of metal nanoclusters. The coordination chemistry of ligands used in the synthesis of metal nanoclusters is crucial in determining their overall shape, metal arrangement, surface ligand binding structure, chirality and also metal exposure. Detailed discussions are given in the following four different systems: (1) The co-use of phosphines and thiolates with rich coordination structures (2 to 4-coordinated) helps to control the formation of a sequence of Ag nanoclusters with a near-perfectly cubic shape; (2) The metal arrangements and surface structures of AuCu clusters highly depend on metal precursors and counter cations used in the synthesis; (3) Metal clusters with intrinsic chirality are readily prepared by introducing chiral ligands or counterions, making it possible to obtain optically active enantiomers and understand the origin of chirality of metal nanoclusters; (4) The variation of metal exposure of the inner metal core of metal nanocluster can be controlled by the surface ligand coordination structure. Such capabilities to manipulate the surface structure of metal nanoclusters allow the creation of model systems for investigating the structure−reactivity relationship of metal nanomaterials. Several important examples are then discussed to highlight the importance of ligand coordination chemistry in tuning the surface reactivity and catalysis of metal nanoclusters. For example, bulky thiolates on Ag are demonstrated to be more labile than small thiolates for making metal nanoclusters with both enhanced ligand exchange capability and catalysis. Alkynyl ligands can be thermally released from metal nanoclusters more easily than thiolates and halides while maintaining the overall structure, thereby serving as ideal systems for understanding the promoting effect of surface stabilizers on catalysis. Finally, we provide ...

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Section: Surface Reactivities and Catalytic Activities Of Metal Nanoc...mentioning

confidence: 99%

Surface Chemistry of Atomically Precise Coinage–Metal Nanoclusters: From Structural Control to Surface Reactivity and Catalysis

2018

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“…Though most of the commonly used thiolate or alkynyl ligands possess strong coordination ability to metals,w eakly coordinating ligands (such as CrO 4 À ,S bF 6 À )c an also be introduced to metal nanoclusters through rational design. [10] Taking advantage of these weakly coordinated sites,f unctional or chiral ligands have been introduced on the Ag I clusters. [11] It occurs to us that ah ighly promising way to realize controls of properties of clusters is through surface modification via weakly coordinated sites which possess high reactivities.I nspired by this,w eh ave used am ixed ligands strategy (with bulky thiolates,p hosphines and small solvent ligands), to synthesize ac hiral silver cluster,[ Ag 14 (SPh-(CF 3 ) 2 ) 12 (PPh 3 ) 4 (DMF) 4 ]( abbreviated hereafter as Ag 14 -DMF,H SPh(CF 3 ) 2 = 3,5-bis(trifluoromethyl)benzenethiol).…”

Section: Introductionmentioning

confidence: 99%

Enhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties

et al. 2021

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Surface ligands play critical roles in determining the surface properties of metal clusters.H owever,m odulating the properties and controlling the surface structure of clusters through surface-capping-agent displacement is challenging. Herein, [Ag 14 (SPh(CF 3 ) 2 ) 12 (PPh 3 ) 4 (DMF) 4 ]( Ag 14 -DMF; DMF = N,N-dimethylformamide), with weakly coordinated DMF ligands on surface silver sites,w as synthesized by am ixed-ligands strategy.O wing to the high surface reactivity of Ag 14 -DMF,the surface ligands are labile,easily dissociated or exchanged by other ligands.Based on the enhanced surface reactivity,easy modulation of the optical properties of Ag 14 by reversible "on-off"D MF ligation was realized. When chiral amines were introduced to as-prepared products,a ll eight surface ligands were replaced by amines and the racemic Ag 14 clusters were converted to optically pure homochiral Ag 14 clusters as evidenced by circular dichroism (CD) activity and single-crystal X-raydiffraction (SCXRD). This work provides anew insight into modulation of the optical properties of metal clusters and atomically precise homochiral clusters for specific applications are obtained.

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“…D ue to the esthetic structures and a plethora of promising properties, silver nanoclusters have emerged as a hot topic garnering great interests over the last decade. [1][2][3][4][5][6][7][8][9][10][11][12] However, their synthetic chemistry is still in the embryo, and trial and error is now the most popular synthetic routine. Regarding their assembly, protecting ligand is one of the most important prerequisites we must consider, and the widely recognized candidates are thiols, alkynes, and phosphines, or their combinations.…”

mentioning

confidence: 99%

A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster

et al. 2020

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Thiacalix [4]arenes as a family of promising ligands have been widely used to construct polynuclear metal clusters, but scarcely employed in silver nanoclusters. Herein, an aniontemplated Ag 88 nanocluster (SD/Ag88a) built from p-tert-butylthiacalix[4]arene (H 4 TC4A) is reported. Single-crystal X-ray diffraction reveals that C 4 -symmetric SD/Ag88a resembles a metal-organic super calix comprised of eight TC4A 4− as walls and 88 silver atoms as base, which can be deconstructed to eight [CrO 4 @Ag 11 (TC4A)(EtS) 4 (OAc)] secondary building units arranged in an annulus encircling a CrO 4 2− in the center. Local and global anion template effects from chromates are individually manifested in SD/Ag88a. The solution stability and hierarchical assembly mechanism of SD/Ag88a are studied by using electrospray mass spectrometry. The Ag 88 nanocluster represents the highest nuclearity metal cluster capped by TC4A 4− . This work not only exemplify the specific macrocyclic effects of TC4A 4− in the construction of silver nanocluster but also realize the shape heredity of TC4A 4− to overall silver super calix.

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An Alkynyl‐Stabilized Pt₅Ag₂₂ Cluster Featuring a Two‐Dimensional Alkynyl–Platinum “Crucifix Motif”

Cited by 18 publications

References 57 publications

Surface Chemistry of Atomically Precise Coinage–Metal Nanoclusters: From Structural Control to Surface Reactivity and Catalysis

Surface Chemistry of Atomically Precise Coinage–Metal Nanoclusters: From Structural Control to Surface Reactivity and Catalysis

Enhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties

A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster

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An Alkynyl‐Stabilized Pt5Ag22 Cluster Featuring a Two‐Dimensional Alkynyl–Platinum “Crucifix Motif”

Cited by 18 publications

References 57 publications

Surface Chemistry of Atomically Precise Coinage–Metal Nanoclusters: From Structural Control to Surface Reactivity and Catalysis

Surface Chemistry of Atomically Precise Coinage–Metal Nanoclusters: From Structural Control to Surface Reactivity and Catalysis

Enhanced Surface Ligands Reactivity of Metal Clusters by Bulky Ligands for Controlling Optical and Chiral Properties

A hierarchically assembled 88-nuclei silver-thiacalix[4]arene nanocluster

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An Alkynyl‐Stabilized Pt₅Ag₂₂ Cluster Featuring a Two‐Dimensional Alkynyl–Platinum “Crucifix Motif”