Atomically Precise Alloy Nanoclusters

Kawawaki, Tokuhisa; Imai, Yuki; Suzuki, Daiki; Kato, Susumu; Kobayashi, Ibuki; Suzuki, Taiyo; Kaneko, Ryo; Hossain, Sakiat; Negishi, Yuichi

doi:10.1002/chem.202001877

Cited by 75 publications

(59 citation statements)

References 251 publications

(1,138 reference statements)

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“…Random alloy clusters represent an alternative to site-specific doping and metal segregation that can be observed when different metals are mixed in the molecular and nanoscale domain. 14 − 23 , 29 − 31 …”

Section: Discussionmentioning

confidence: 99%

Heterometallic Ni–Pt Chini-Type Carbonyl Clusters: An Example of Molecular Random Alloy Clusters

et al. 2021

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The direct reactions of homometallic [Ni 6 (CO) 12 ] 2– and [Pt 6 (CO) 12 ] 2– Chini carbonyl clusters result in heterometallic Ni–Pt Chini-type clusters of the general formula [Pt 6– x Ni x (CO) 12 ] 2– ( x = 0–6). Their molecular structures have been determined by single-crystal X-ray diffraction (SC-XRD), showing a common octahedral (staggered, D 3 d ) structure analogous to that of [Ni 6 (CO) 12 ] 2– , whereas [Pt 6 (CO) 12 ] 2– displays a trigonal-prismatic (eclipsed, D 3 h ) structure. This structural change after replacing one single Pt with Ni may be classified as an alloying effect, and it has been theoretically investigated by DFT methods. Spectroscopic (IR and 195 Pt and 13 C NMR) and ESI-MS studies indicate that mixtures of [Pt 6– x Ni x (CO) 12 ] 2– ( x = 0–6) clusters are actually present in solution, whose compositions may be varied in an almost continuous way. Thus, they may be viewed as random alloy clusters whose overall compositions depend on the stoichiometry of the reagents.

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Section: Discussionmentioning

confidence: 99%

Heterometallic Ni–Pt Chini-Type Carbonyl Clusters: An Example of Molecular Random Alloy Clusters

et al. 2021

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“…Bimetallic NCs often show unique properties compared to homo‐metallic ones owing to the synergy between constituent metals and the modified electronic structure [2–5] . There have been reports of incorporating different heterometals into gold NCs [3, 6–10] . These bimetallic NCs are also applied in bio‐sensing and catalysis with significantly enhanced functionalities [2, 11–17] …”

Section: Figurementioning

confidence: 99%

Total Structure of Bimetallic Core–Shell [Au₄₂Cd₄₀(SR)₅₂]²⁻ Nanocluster and Its Implications

Tang

Cheng

et al. 2021

Angewandte Chemie

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Bimetallic core–shell nanostructures hold great promise in elucidating the bimetallic synergism. However, it remains a challenge to construct atomically precise core–shell with high‐valence active metals on the gold surface. In this work, we report the total structure of a [Au42Cd40(SR)52]2− core–shell nanocluster and multiple implications. Single crystal X‐ray diffraction (SCXRD) reveals that the structure possesses a two‐shelled Au6@Au36 core and a closed cadmium shell of Cd40, and the core–shell structure is then protected by 52 thiolate (‐SR) ligands. The composition of the nanocluster is further confirmed by electrospray ionization mass spectrometry (ESI‐MS). A catalytic test for styrene oxidation and a comparison with relevant nanoclusters reveal the surface effect on the catalytic activity and selectivity.

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“…[49] For an overview of the effects brought about by decorating AuNCs with foreign-metal atoms, we refer the readert oavery recent review. [50] It should be noted, however,t hat despite the increasing number of these studies, the control over the number of doping metal atoms (e.g.,A g) [51] is still challenging. Regarding monodoping, our group has demonstrated with ac ombination of NMR spectroscopy, electrochemistry,and mass spectrometry data that independently of the synthetic methodt he position of both Cd and Hg is alwayso nt he icosahedron, [52] rather than elsewhere (centero rs taples) as often described.Afuture goal is to tailor the heteroatom position andinvestigate the effect of the insertion of foreign metals with peculiar magnetic (Mn, Fe) or optical (lanthanides) properties.…”

Section: Nc Building Blocks and Design Rulesmentioning

confidence: 99%

Atomically Precise Metal Nanoclusters: Novel Building Blocks for Hierarchical Structures

Bonacchi

Antonello

Dainese

et al. 2020

Chemistry A European J

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Atomically precise ligand-protected nanoclusters (NCs) constitutea ni mportant class of compounds that exhibit well-defineds tructures and, when sufficiently small, evident molecular properties. NCs provide versatile building blocks to fabricate hierarchical superstructures. The assembly of NCs indeed offers opportunities to devise new materials with given structures and able to carry out specific functions. In this Concept article, we highlight the possibilities offered by NCs in which the physicochemical properties are controlled by the introductiono ff oreign metal atoms and/or modification of the compositiono f the capping monolayer with functional ligands. Different approaches to assemble NCs into dimers and higher hierarchy structures and the corresponding changes in physicochemical properties are also described.

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Atomically Precise Alloy Nanoclusters

Abstract: To kuhisa Kawawaki, [a, b, c] Yukari Imai, [a] Daiki Suzuki, [a] ShunK ato, [a] Ibuki Kobayashi, [a] Ta iyoS uzuki, [a] Ryo Kaneko, [a] SakiatH ossain, [a] and YuichiN egishi* [a, b, c]

Cited by 75 publications

References 251 publications

Heterometallic Ni–Pt Chini-Type Carbonyl Clusters: An Example of Molecular Random Alloy Clusters

Heterometallic Ni–Pt Chini-Type Carbonyl Clusters: An Example of Molecular Random Alloy Clusters

Total Structure of Bimetallic Core–Shell [Au₄₂Cd₄₀(SR)₅₂]²⁻ Nanocluster and Its Implications

Atomically Precise Metal Nanoclusters: Novel Building Blocks for Hierarchical Structures

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Atomically Precise Alloy Nanoclusters

Abstract: To kuhisa Kawawaki, [a, b, c] Yukari Imai, [a] Daiki Suzuki, [a] ShunK ato, [a] Ibuki Kobayashi, [a] Ta iyoS uzuki, [a] Ryo Kaneko, [a] SakiatH ossain, [a] and YuichiN egishi* [a, b, c]

Cited by 75 publications

References 251 publications

Heterometallic Ni–Pt Chini-Type Carbonyl Clusters: An Example of Molecular Random Alloy Clusters

Heterometallic Ni–Pt Chini-Type Carbonyl Clusters: An Example of Molecular Random Alloy Clusters

Total Structure of Bimetallic Core–Shell [Au42Cd40(SR)52]2− Nanocluster and Its Implications

Atomically Precise Metal Nanoclusters: Novel Building Blocks for Hierarchical Structures

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Total Structure of Bimetallic Core–Shell [Au₄₂Cd₄₀(SR)₅₂]²⁻ Nanocluster and Its Implications