All-Carboxylate-Protected Superatomic Silver Nanocluster with an Unprecedented Rhombohedral Ag<sub>8</sub> Core

Liu, Kuan‐Guan; Gao, Xueqin; Liu, Tongyu; Hu, Mao‐Lin; Jiang, De‐en

doi:10.1021/jacs.0c06682

Cited by 90 publications

(47 citation statements)

References 53 publications

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“…[4][5][6][7][8][9] So far, only one homoleptic twoelectron NC, [Ag 8 (pfga) 6 ] 6À , is known. [10] In the present contribution, we report the isolation of a homoleptic, dithiolate-stabilized Ag 10 two-electron NC whose metal core is totally different from the above mentioned structures. Whereas most of the above-mentioned two-electron species were prepared with borohydride, [4,6,9] silane, [5] or DMF [7,10] as reducing agents (Supporting Information, Table S1), controlling the amount of reductants used in their synthesis to avoid the formation of 8-electron species can be problematic.…”

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confidence: 80%

“…The stability and structure of NCs can often be rationalized within the concept of superatom and its magic closed‐shell electron counts of 2, 8, 18, 20, 34, 40, 58 [2] . Whereas the majority of reported silver superatoms are 8‐electron species, [3] examples of two‐electron superatoms are surprisingly fewer (Supporting Information, Table S1) [4–10] . The first one, Ag 14 (SC 6 H 3 F 2 ) 12 (PPh 3 ) 8 , was published in 2013 [4] .…”

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confidence: 99%

“…The tetracapped tetrahedral [Ag 8 ] 6+ core is also well represented [7e] . Other examples display rhombohedral [Ag 8 ] 6+ , [10] fcc‐packed [Ag 7 ] 5+ , [8] or anti‐cuboctahedral [Ag 13 ] 11+ [9] cores. Most of them are co‐protected by two or more types of ligands such as phosphines, thiolates, alkynyls, or polyoxometalates [4–9] .…”

Section: Figurementioning

confidence: 99%

“…[6] Additional two-electron Ag NCs were reported only recently, thus becoming a hot topic in the NC community. [7][8][9][10] Most of the two-electron Ag NCs listed in the Supporting Information, Table S1 have an octahedral [Ag 6 ] 4+ superatomic core, and the other silver atoms of the cluster, if any, are formally Ag I . [4,5,7] The tetracapped tetrahedral [Ag 8 ] 6+ core is also well represented.…”

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confidence: 99%

“…[2] Whereas the majority of reported silver superatoms are 8-electron species, [3] examples of two-electron superatoms are surprisingly fewer (Supporting Information, Table S1). [4][5][6][7][8][9][10] The first one, Ag 14 (SC 6 H 3 F 2 ) 12 (PPh 3 ) 8 , was published in 2013. [4] It was followed in the same year by [Ag 6 (g-H 2 SiW 10 O 36 ) 2 ] 8À , [5] and Ag 16 (dppe) 4 (SC 6 H 3 F 2 ) 14 .…”

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confidence: 99%

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A Two‐Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride

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Rational syntheses under controllable reducing conditions in the preparation of superatoms with cluster electron number not exceeding two are challenging. Herein a dithiolate-stabilized two-electron silver nanocluster, Ag 10 -{S 2 P(O i Pr) 2 } 8 (1), is isolated via a self-redox reaction of Ag 7 (H){S 2 P(O i Pr) 2 } 6 without adding extra reducing agents. The metal framework of Ag 7 , a bicapped trigonal bipyramid, is highly correlated to that of Ag 10 , suggesting Ag 7 (H){S 2 P-(O i Pr) 2 } 6 acts as both reducing agent and template in cluster growth. 1 is highly fluorescent at ambient temperature and TD-DFT calculations indicate that the emission is of 1P x !1S nature.

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confidence: 80%

Section: Figurementioning

confidence: 99%

Section: Figurementioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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A Two‐Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride

et al. 2021

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In Situ Synthesis of Bismuth Nanoclusters within Carbon Nano‐Bundles from Metal–Organic Framework for Chloride‐Driven Electrochemical Deionization

Liu

Wang

Yao

et al. 2021

Adv Funct Materials

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Ultrasmall metal nanoclusters (MNCs, <3 nm) have emerged as a novel class of functional nanomaterials. Different from the prosperous development of noble MNCs, the fabrication of non‐noble MNCs remains a major challenge, which greatly curtails the advance of relevant application fields. Herein the authors put forward an in situ synthesis strategy of bismuth nanoclusters (Bi NCs) within carbon nano‐bundles (Bi NCs@CNBs) by simply carbonizing the Bi‐containing metal–organic framework (Bi‐MOF), and deploy it as a Cl− capturing electrode for electrochemical deionization (EDI) towards the relief of global freshwater scarcity. Of note, as a “killing two birds with one stone” strategy, the Bi‐MOF not only makes the in situ formation of Bi NCs possible but also provides a reinforcing “carbon shell” for better electronic conductivity and structural stability. As a result, the Bi NCs@CNB‐based EDI system displays ultrafast desalination (0.52 mg g−1 s−1) with outstanding cycling stability, which is beneficial from the ultrasmall size of the electrode material and cannot be achieved by large‐sized Bi nanoparticle‐based system. This work is interesting because it unprecedentedly introduces ultrasmall MNCs into EDI to manipulate the surface‐controlled Cl− storage for ultrafast EDI, boosting the advances of both non‐noble MNCs and their application in EDI.

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Tunable Luminescence from Stable Silver Nanoclusters Confined in Microporous Zeolites

Romolini

Steele

Hofkens

et al. 2021

Advanced Optical Materials

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properties associated with nanoclusters' molecule-like structure and energetics. Most notably, metal nanoclusters rose to research prominence in connection to the discovery of outstanding optoelectronic properties and have found practical application within catalysis, bioimaging, lighting and molecular sensing. [1][2][3][4][5][6] However, nanocluster' stabilization remains a significant impediment owing to their tendency to merge and form ever-larger aggregates at the loss of their interesting properties. Therefore, research efforts have been devoted to developing novel synthetic strategies to stabilize isolated metal nanoclusters; [7] popular approaches have often taken the form of using organic scaffolds such as DNA/RNA, proteins, and polymers. [8][9][10][11][12][13][14][15][16] The use of organic molecules gives rise to high synthesis yields, good luminescence performance, and strong compatibility with living organism, making them excellent candidates as fluorophores. Unfortunately, a main drawback is their poor long-term stability, especially in solid form, hindering their application, e.g., within lighting devices. On the other hand, template-mediated strategies based on the self-organization of the metal nanocluster within a confined volume (so-called "ship-in-a-bottle" approach) provide a promising alternative, one where the size and shape of the final metal nanocluster are dictated by the spatial restrictions imposed by the rigid host nanostructure. [17] To date, common templating structures have included glass matrices, [18] metal-organic frameworks, [19] and porous aluminosilicate zeolite crystals. [20] Here, we will shine light on zeolites as a promising scaffold for the assembly of highly luminescent and functional silver nanoclusters (Ag-NCs) within their (nano)porous interior (Figure 1a-c). As a host framework, zeolites possess molecular-sized channels and cages which enable them to confine molecules or metal (oxide) clusters inside their crystalline interior in a controlled fashion. Moreover, the framework is negatively charged, requiring counter-balancing extra-framework cations, which can be easily replaced through simple exchange methods. As shown in Figure 1d, forming the caged Ag-NCs involves a scalable bottom-up approach, whereby Ag + ions are made to self-assemble into nanoclusters via energy-driven activation (thermal treatment, photoactivation, or X-rays irradiation). Once the cluster is assembled, its optical response can be further tuned by the intentional exchange of additional guest

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All-Carboxylate-Protected Superatomic Silver Nanocluster with an Unprecedented Rhombohedral Ag₈ Core

Cited by 90 publications

References 53 publications

A Two‐Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride

A Two‐Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride

In Situ Synthesis of Bismuth Nanoclusters within Carbon Nano‐Bundles from Metal–Organic Framework for Chloride‐Driven Electrochemical Deionization

Tunable Luminescence from Stable Silver Nanoclusters Confined in Microporous Zeolites

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All-Carboxylate-Protected Superatomic Silver Nanocluster with an Unprecedented Rhombohedral Ag8 Core

Cited by 90 publications

References 53 publications

A Two‐Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride

A Two‐Electron Silver Superatom Isolated from Thermally Induced Internal Redox Reaction of A Silver(I) Hydride

In Situ Synthesis of Bismuth Nanoclusters within Carbon Nano‐Bundles from Metal–Organic Framework for Chloride‐Driven Electrochemical Deionization

Tunable Luminescence from Stable Silver Nanoclusters Confined in Microporous Zeolites

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All-Carboxylate-Protected Superatomic Silver Nanocluster with an Unprecedented Rhombohedral Ag₈ Core