Reconstructing the Surface of Gold Nanoclusters by Cadmium Doping

Li, Qi; Lambright, Kelly J.; Taylor, Michael; Kirschbaum, Kristin; Luo, Tian‐Yi; Zhao, Jianbo; Mpourmpakis, Giannis; Mokashi-Punekar, Soumitra; Rosi, Nathaniel L.; Jin, Rongchao

doi:10.1021/jacs.7b11491

Cited by 91 publications

(118 citation statements)

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“…Li et al reported that Cd doping can induce reconstruction of the surface of gold nanoclusters. [234] For example, the structure of [Au 19 Cd 2 (SR) 16 ] − (SR = S-c-C 6 H 11 ) shows one pair of Cd[Au(SR) 2 ] 3 staple motifs on the two opposite sides of the kernel (Figure 15a). In each Cd[Au(SR) 2 ] 3 motif, three monomeric Au(SR) 2 are merged at the Cd atom to form a "paw-like" configuration in quasi-C 3 symmetry (Figure 15a, inset (Figure 15b), [235] only one Cd[Au(SR) 2 ] 3 is identified on the surface, and one CdSH unit as well; thus, the single motifs contribute to the chirality of the bimetal Au 20 Cd 4 cluster.…”

Section: Cd-thiolate Surface Structuresmentioning

confidence: 99%

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

et al. 2020

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In chemical science, chirality is indeed one of the most extensively studied phenomena. A chiral molecule possesses a pair of enantiomers and sometimes, only one of the enantiomers is effective as a functional unit or drug. [1,2] The mechanism on how the notorious enantiomers of thalidomide lead to teratogenic newborns has been revealed recently. [3] Chirality in coordination complexes has also been generalized in detail. [4] A classic example of molecules with point chirality is that it contains an asymmetric sp 3 carbon atom which is attached with four different atoms or groups. Such a molecule is not superimposable with its mirror image, and for a simple coordination complex, a metal atom-which is at the centerserves as the role of the chiral carbon (i.e., point chirality). As a result, the relative spatial arrangement of the substituents gives either a clockwise or an anticlockwise order, corresponding to the R and S enantiomers. Of note, the R/S notation of chirality has no fixed relation to the d/l notation (for sugars and amino acids). More generally speaking, chiral object is lack of S n symmetry elements; in other words, if a mirror plane (σ) and inversion (i) are both missing in the object, then it becomes chiral. From this definition, irregular objects are all chiral. Objects of C n (with n-fold axis) or D n (with C 2 axis perpendicular to the n-fold axis) symmetry are much more appealing as long-range order is created. Along with organic chiral molecules, [2] chiral complexes, [4] and chiral supramolecular systems with autonomous self-assembly generated by intermolecular noncovalent interactions have been discussed thoroughly in previous reviews. [5-9] Chiral inorganic nanostructures, with intermediate sizes between molecules of Å and objects of micrometers, are of critical significance owing to their tremendous applications in chiral catalysis, chiroptical metamaterials, enantioseparation, biomolecular and enantiomer sensing, as well as medicine. [10-12] For chiral semiconductor nanoparticles (NPs), commonly called quantum dots (QDs), such as cadmium chalcogenides, the chiral surface ligands are attached onto the QDs through covalent bonds, [13-17] and many applications can be designed. [18] The interactions of chiral moieties attached on graphene NPs lead to their helical assembly, enriching the optical and electronic properties of these chiral nanostructures and facilitating their applications. [19-21] The studies on chiral metal NPs greatly overwhelm those on the semiconductor counterparts. Metal NPs are known to have Chirality is ubiquitous in nature and occurs at all length scales. The development of applications for chiral nanostructures is rising rapidly. With the recent achievements of atomically precise nanochemistry, total structures of ligand-protected Au and other metal nanoclusters (NCs) are successfully obtained, and the origins of chirality are discovered to be associated with different parts of the cluster, including the surface ligands (e.g., swirl patterns), the organic-inorganic in...

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Section: Cd-thiolate Surface Structuresmentioning

confidence: 99%

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

et al. 2020

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“…Single‐crystal X‐ray diffraction revealed that the recrystallization crystal has the same metal core structure with Eu 52 Ni 56 , suggesting the integrity of Eu 52 Ni 56 after hydrothermal reaction. Energy dispersive X‐ray spectroscopy (EDX) elemental mapping of the crystal indicates that some of the Ni 2+ was replaced by Cd 2+ during the hydrothermal reaction and then formed the metal exchanged heterometallic 4f–3d–4d cluster [Ln 52 Ni 56− x Cd x (IDA) 48 (OH) 154 (H 2 O) 38 ] 18+ (labeled as Ln 52 Ni 56− x Cd x ) (Figure S5, S6) . The inductively coupled plasma spectrometry (ICP‐MS) results demonstrate that the substitution percentage is approximately 20 % (Table S2).…”

Section: Methodsmentioning

confidence: 99%

Integration of Lanthanide–Transition‐Metal Clusters onto CdS Surfaces for Photocatalytic Hydrogen Evolution

et al. 2018

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Heterometallic lanthanide–transition‐metal (4f–3d) clusters with well‐defined crystal structures integrate multiple metal centers and provide a platform for achieving synergistic catalytic effects. Herein, we present a strategy for enhanced hydrogen evolution by loading atomically precise 4f–3d clusters Ln52Ni56 on a CdS photoabsorber surface. Interestingly, some Ni2+ ions in the clusters Ln52Ni56 were exchanged by the Cd2+ to form Ln52Ni56−xCdx/CdS composites. Photocatalytic studies show that the efficient synergistic multipath charge separation and transfer from CdS to the Eu52Ni56−xCdx cluster enable high visible‐light‐driven hydrogen evolution at 25 353 μmol h−1 g−1. This work provides the strategy to design highly active photocatalytic hydrogen evolution catalysts by assembling heterometallic 4f–3d clusters on semiconductor materials.

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“…This readily means that Cd(SR) 2 may prompt a similar oxidation‐induced size conversion reaction of [Au 23 (SR) 16 ] − (toward [Au 28 (SR) 20 ] 0 ), which takes place concurrently with a substitution reaction of 2 Au → 1 Cd. Isoelectronic size conversion from [Au 23 (SR) 16 ] − to [Au 19 Cd 2 (SR) 16 ] − could also be accomplished via similar substitution of four surface Au atoms of the former by two Cd heteroatoms …”

Section: Synthesis Of Metal Ncs Via Cluster‐conversion Strategymentioning

confidence: 99%

Engineering Functional Metal Materials at the Atomic Level

et al. 2018

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With continuous research efforts devoted into synthesis and characterization chemistry of functional nanomaterials in the past decades, the development of metal materials is stepping into a new era, where atom-by-atom customization of property-dictating structural attributes is expected. Herein, the state-of-the-art modulation of functional metal nanomaterials at the atomic level, by size- and structure-controlled synthesis of thiolate-protected metal (e.g., Au and Ag) nanoclusters (NCs), is exemplified. Metal NCs are ultrasmall (<3 nm) particles with hierarchical primary, secondary, and tertiary structures, reminiscent of natural proteins or enzymes. Given the proven dependence of their physicochemical properties on their size and structure, documented synthetic methodologies delivering NCs with atomic-level monodispersity and tailorable size and structural attributes at individual hierarchical levels are categorized and discussed. Such assured atomic-level modulation could confer metal NCs with novel application opportunities in diverse fields, which are also exemplified by their size- and structure-dictated catalytic and biomedical performance. The precise synthesis and application chemistry developed based on the hierarchical structure scheme of metal NCs could increase the acceptance of metal NCs as a new family of functional materials.

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Reconstructing the Surface of Gold Nanoclusters by Cadmium Doping

Cited by 91 publications

References 44 publications

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Integration of Lanthanide–Transition‐Metal Clusters onto CdS Surfaces for Photocatalytic Hydrogen Evolution

Engineering Functional Metal Materials at the Atomic Level

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