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This perspective highlights advances in the preparation and understanding of metal nanoclusters stabilized by organic ligands with a focus on N-heterocyclic carbenes (NHCs). We demonstrate the need for a clear understanding of the relationship between NHC properties and their resulting metal nanocluster structure and properties. We emphasize the importance of balancing nanocluster stability with the introduction of reactive sites for catalytic applications and the importance of a better understanding of how these clusters interact with their environments for effective use in biological applications. The impact of atom-scale simulations, development of atomic interaction potentials suitable for large-scale molecular dynamics simulations, and a deeper understanding of the mechanisms behind synthetic methods and physical properties (e.g., the bright fluorescence displayed by many clusters) are emphasized.
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Density functional theory is used to study geometric, energetic, and electronic properties of metal-ligand bonds in a series of group-11 metal complexes and ligand-protected metal clusters. We study complexes as the forms of M-L (L = SCH3, SC8H9, PPh3, NHCMe, NHCEt, NHCiPr, NHCBn, CCMe, CCPh) and L1-M-L2 (L1 = NHCBn, PPh3, and L2 = CCPh). Furthermore, we study clusters denoted as [M13L6Br6]- (L = PPh3, NHCMe, NHCEt, NHCiPr, NHCBn). The systems were studied at the standard GGA level using the PBE functional and including vdW corrections via BEEF-vdW. Generally, Au has the highest binding energies, followed by Cu and Ag. PBE and BEEF-vdW functionals show the order Ag-L > Au-L > Cu-L for bond lengths in both M-L complexes and metal clusters. In clusters, the smallest side group (CH3) in NHCs leads to the largest binding energy whereas no significant variations are seen concerning different side groups of NHC in M-L complexes. By analyzing the projected density of states and molecular orbitals in complexes and clusters, the M-thiolate bonds were shown to have σ and π bond characteristics whereas phosphines and carbenes were creating σ bonds to the transition metals. Interestingly, this analysis revealed divergent behavior for M-alkynyl complexes: while the CCMe group displayed both σ and π bonding features, the CCPh ligand was found to possess only σ bond properties in direct head-to-head binding configuration. Moreover, synergetic effects increase the average binding strength to the metal atom significantly in complexes of two different ligands and underline the potential of adding Cu to synthesize structurally richer cluster systems. This study helps in understanding the effects of different ligands on the stability of M-L complexes and clusters and suggests that PPh3 and NHCs-protected Cu clusters are most stable after Au clusters.
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Understanding the dynamics of Förster resonance energy transfer (FRET) in fluorophore-functionalized nanomaterials is critical for developing and utilizing such materials in biomedical imaging and optical sensing applications. However, structural dynamics of noncovalently bound systems have a significant effect on the FRET properties affecting their applications in solutions. Here, we study the dynamics of the FRET in atomistic detail by disclosing the structural dynamics of the noncovalently bound azadioxotriangulenium dye (KU) and atomically precise gold nanocluster (Au25(p-MBA)18, p-MBA = para-mercaptobenzoic acid) with a combination of experimental and computational methods. Two distinct subpopulations involved in the energy transfer process between the KU dye and the Au25(p-MBA)18 nanoclusters were resolved by time-resolved fluorescence experiments. Molecular dynamics simulations revealed that KU is bound to the surface of Au25(p-MBA)18 by interacting with the p-MBA ligands as a monomer and as a π-π stacked dimer where the center-to-center distance of the monomers to Au25(p-MBA)18 is separated by â¼0.2 nm, thus explaining the experimental observations. The ratio of the observed energy transfer rates was in reasonably good agreement with the well-known 1/R6 distance dependence for FRET. This work discloses the structural dynamics of the noncovalently bound nanocluster-based system in water solution, providing new insight into the dynamics and energy transfer mechanism of the fluorophore-functionalized gold nanocluster at an atomistic level.
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DNA-stabilized silver nanoclusters (AgN-DNAs) are known to have one or two DNA oligomer ligands per nanocluster. Here, we present the first evidence that AgN-DNA species can possess additional chloride ligands that lead to increased stability in biologically relevant concentrations of chloride. Mass spectrometry of five chromatographically isolated near-infrared (NIR)-emissive AgN-DNA species with previously reported X-ray crystal structures determines their molecular formulas to be (DNA)2[Ag16Cl2]8+. Chloride ligands can be exchanged for bromides, which red-shift the optical spectra of these emitters. Density functional theory (DFT) calculations of the 6-electron nanocluster show that the two newly identified chloride ligands were previously assigned as low-occupancy silvers by X-ray crystallography. DFT also confirms the stability of chloride in the crystallographic structure, yields qualitative agreement between computed and measured UV-vis absorption spectra, and provides interpretation of the 35Cl-nuclear magnetic resonance spectrum of (DNA)2[Ag16Cl2]8+. A reanalysis of the X-ray crystal structure confirms that the two previously assigned low-occupancy silvers are, in fact, chlorides, yielding (DNA)2[Ag16Cl2]8+. Using the unusual stability of (DNA)2[Ag16Cl2]8+ in biologically relevant saline solutions as a possible indicator of other chloride-containing AgN-DNAs, we identified an additional AgN-DNA with a chloride ligand by high-throughput screening. Inclusion of chlorides on AgN-DNAs presents a promising new route to expand the diversity of AgN-DNA structure-property relationships and to imbue these emitters with favorable stability for biophotonics applications.
Asunto(s)
Cloruros , Plata , Cloruros/química , Plata/química , Ligandos , Cristalografía por Rayos X , ADN/químicaRESUMEN
Fragmentation dynamics of ligated coinage metal clusters reflects their structural and bonding properties. So far methodological challenges limited probing structures of the fragments. Herein, we resolve the geometric structures of the primary fragments of [Ag29 L12 ]3- , i.e. [Ag24 L9 ]2- , [Ag19 L6 ]- and [Ag5 L3 ]- (L is 1,3-benzene dithiolate). For this, we used trapped ion mobility mass spectrometry to determine collision cross sections of the fragments and compared them to structures calculated by density functional theory. We also report that following two sequential [Ag5 L3 ]- elimination steps, further dissociation of [Ag19 L6 ]- also involves a new channel of Ag2 loss and Ag-S and C-S bond cleavages. This reflects a competition between retaining the electronic stability of 8 e- superatom cluster cores and increasing steric strain of ligands and staples. These results are also of potential interest for future soft-landing deposition studies aimed at probing catalytic behavior of Ag clusters on supports.
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Understanding the origin of chirality in the nanostructured materials is essential for chiroptical and catalytic applications. Here we report a chiral AgCu superatomic cluster, [Ag22 Cu7 (C≡CR)16 (PPh3 )5 Cl6 ](PPh4 ), Ag22 Cu7 , protected by an achiral alkynyl ligand (HC≡CR: 3,5-bis(trifluoromethyl)phenylacetylene). Its crystal structure comprises a rare interpenetrating biicosahedral Ag17 Cu2 core, which is stabilized by four different types of motifs: one Cu(C≡CR)2 , four -C≡CR, two chlorides and one helical Ag5 Cu4 (C≡CR)10 (PPh3 )5 Cl4 . Structural analysis reveals that Ag22 Cu7 exhibits multiple chirality origins, including the metal core, the metal-ligand interface and the ligand layer. Furthermore, the circular dichroism spectra of R/S-Ag22 Cu7 are obtained by employing appropriate chiral molecules as optical enrichment agents. DFT calculations show that Ag22 Cu7 is an eight-electron superatom, confirm that the cluster is chirally active, and help to analyze the origins of the circular dichroism.
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Herein we report the first chiral Au10 nanoclusters stabilized by chiral bis N-heterocyclic carbene (bisNHC) ligands. ESI-MS and single-crystal X-ray crystallography confirmed the molecular formula to be [Au10(bisNHC)4Br2](O2CCF3)2. The chiral Au10 nanocluster adopts a linear edge-shared tetrahedral geometry with a prolate shape. DFT calculations provide insight into the electronic structure, optical absorption, and circular dichroism (CD) characteristics of this unique Au10 nanocluster. CD spectra demonstrate chirality transfer from the chiral bisNHC ligand to the inner Au10 nanocluster core. Examination of ESI-MS and UV-vis spectra show that cluster [Au9(bisNHC)4Br]Br2 is formed initially and then transformed into the Au10 nanocluster in solution.
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The complexity of heterogeneous metal catalysts makes it challenging to gain insights into their catalytic mechanisms. Thus, there exists a huge gap between heterogeneous catalysis and organometallic catalysis. With the success in the preparation of highly robust atomically precise metal nanocluster catalysts (i.e., [Au16(NHC-1)5(PA)3Br2]3+ and [Au17(NHC-1)4(PA)4Br4]+, where NHC-1 is a bidentate NHC ligand, and PA is phenylacetylide) with surface organometallic motifs anchored on the metallic core, we demonstrate in this work how the metallic core works synergistically with the surface organometallic motifs to enhance the catalysis. More importantly, the discovery allows the development of highly stable and recyclable heterogeneous metal catalysts to achieve efficient hydroamination of alkynes with an extremely low catalyst dosage (0.002 mol %), helping bridge the gap between heterogeneous and homogeneous metal catalysis. The surface modification of metal nanocatalysts with organometallic motifs provides a new design principle of metal catalysts with enhanced catalysis.
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Atomically precise hydrido gold nanoclusters are extremely rare but interesting due to their potential applications in catalysis. By optimization of molecular precursors, we have prepared an unprecedented N-heterocyclic carbene-stabilized hydrido gold nanocluster, [Au24(NHC)14Cl2H3]3+. This cluster comprises a dimer of two Au12 kernels, each adopting an icosahedral shape with one missing vertex. The two kernels are joined through triangular faces, which are capped with a total of three hydrides. The hydrides are detected by electrospray ionization mass spectrometry and nuclear magnetic resonance spectroscopy, with density functional theory calculations supporting their position bridging the six uncoordinated gold sites. The reactivity of this Au24H3 cluster in the electrocatalytic reduction of CO2 is demonstrated and benchmarked against related catalysts.
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High-resolution electrospray ionization ion mobility mass spectrometry has revealed a gas-phase isomer of the ubiquitous, extremely well-studied Au25(SR)18 cluster both in anionic and cationic form. The relative abundance of the isomeric structures can be controlled by in-source activation. The measured collision cross section of the new isomer agrees extremely well with a recent theoretical prediction (Matus, M. F.; et al. Chem. Commun. 2020, 56, 8087) corresponding to a Au25(SR)18- isomer that is energetically close and topologically connected to the known ground-state structure via a simple rotation of the gold core without breaking any Au-S bonds. The results imply that the structural dynamics leading to isomerization of thiolate-protected gold clusters may play an important role in their gas-phase reactions and that isomerization could be controlled by external stimuli.
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Heteroatom-doped metal nanoclusters (NCs) are highly desirable to gain fundamental insights into the effect of doping on the electronic structure and catalytic properties. Unfortunately, their controlled synthesis is highly challenging when the metal atomic sizes are largely different (e.g., Cu and Pt). Here, we design a metal-exchange strategy that enables simultaneous doping and resizing of NCs. Specifically, [Pt2Cu34(PET)22Cl4]2- NC, the first example of a Pt-doped Cu NC, is synthesized by utilizing the unique reactivity of [Cu32(PET)24Cl2H8]2- NC with Pt4+ ions. The single-crystal X-ray structure reveals that two directly bonded Pt atoms occupy the two centers of an unusually interpenetrating, incomplete biicosahedron core (Pt2Cu18), which is stabilized by a Cu16(PET)22Cl4 shell. The molecular structure and composition of the NC are validated by combined experimental and theoretical results. Electronic structure calculations, using the density functional theory, show that the Pt2Cu34 NC is a 10-electron superatom. The computed absorption spectrum matches well with the measured data and allows for assignment of the absorption peaks. The calculations also rationalize energetics for ligand exchange observed in the mass spectrometry data. The synergistic effects induced by Pt doping are found to enhance the catalytic activity of Cu NCs by â¼300-fold in silane to silanol conversion under mild conditions. Furthermore, our synthetic strategy has potential to produce Ni-, Pd-, and Au-doped Cu NCs, which will open new avenues to uncover their molecular structures and catalytic properties.
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Reported herein are the synthesis and structures of two high-nuclearity AuAg nanoclusters, namely, [Au78Ag66(C≡CPh)48Cl8]q- and [Au74Ag60(C≡CPh)40Br12]2-. Both clusters possess a three-concentric-shell Au12@Au42@Ag60 structure. However, the dispositions of the metal atoms, and the ligand coordination modes, of the outermost shells of these clusters are distinctly different. These structural differences reflect the bonding characteristics of the halide ligands. As revealed by density functional theory analysis, these clusters exhibit superatomic electron shell closings at magic numbers of 92 (for q = 4) and 84, respectively, consistent with their spherical shapes. Both clusters exhibit unusual multivalent redox properties.
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The magnetic response of valence electrons in doped gold-based M@Au8L8 q superatoms (M = Pd, Pt, Ag, Au, Cd, Hg, Ir, and Rh; L = PPh3; and q = 0, +1, +2) is studied by calculating the gauge including magnetically induced currents (GIMIC) in the framework of the auxiliary density functional theory. The studied systems include 24 different combinations of the dopant, total cluster charge, and cluster structure (cubic-like or oblate). The magnetically induced currents (both diatropic and paratropic) are shown to be sensitive to the atomic structure of clusters, the number of superatomic electrons, and the chemical nature of the dopant metal. Among the cubic-like structures, the strongest aromaticity is observed in Pd- and Pt-doped M@Au8L8 0 clusters. Interestingly, Pd- and Pt-doping increases the aromaticity as compared to a similar all-gold eight-electron system Au9L8 +1. With the recent implementation of the GIMIC in the deMon2k code, we investigated the aromaticity in the cubic and butterfly-like M@Au8 core structures, doped with a single M atom from periods 5 and 6 of groups IX-XII. Surprisingly, the doping with Pd and Pt in the cubic structure increases the aromaticity compared to the pure Au case not only near the central atom but encompassing the whole metallic core, following the aromatic trend Pd > Pt > Au. These doped (Pd, Pt)@Au8 nanoclusters show a closed shell 1S21P6 superatom electronic structure corresponding to the cubic aromaticity rule 6n + 2.
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Surface ligands play critical roles in determining the surface properties of metal clusters. However, modulating the properties and controlling the surface structure of clusters through surface-capping-agent displacement is challenging. Herein, [Ag14 (SPh(CF3 )2 )12 (PPh3 )4 (DMF)4 ] (Ag14 -DMF; DMF=N,N-dimethylformamide), with weakly coordinated DMF ligands on surface silver sites, was synthesized by a mixed-ligands strategy. Owing to the high surface reactivity of Ag14 -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 Ag14 by reversible "on-off" DMF ligation was realized. When chiral amines were introduced to as-prepared products, all eight surface ligands were replaced by amines and the racemic Ag14 clusters were converted to optically pure homochiral Ag14 clusters as evidenced by circular dichroism (CD) activity and single-crystal X-ray diffraction (SCXRD). This work provides a new insight into modulation of the optical properties of metal clusters and atomically precise homochiral clusters for specific applications are obtained.
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A new alkynylated cluster [Au13 Ag16 (C10 H6 NO)24 ]3- is prepared by a NaBH4 mediated reduction method. The AuAg clusters are confirmed by sophisticated characterization techniques. It has a unique "Aucenter @Ag12 @Au12 Ag4 " metal framework which is protected by 24â atypical alkyne ligands L (L=C10 H6 NO). The ligands construct a unique type of motif L-(Ag)-Au-(Ag)-L at the cluster interface, where the alkyne (C≡C) group of each L was linked by sharing an Au atom through the σ bonds and each C≡C group was discretely connected to a chemically different Ag atom (Agicosahedral /Agcap ) through πâ bonds. The electronic and optical properties of [Au13 Ag16 L24 ]3- were studied. DFT characterized the cluster as a clear 8-electron superatom, and peaks in the optical absorption spectrum were interpreted in terms of the P and D superatom states. The supported Au13 Ag16 L24 /CeO2 catalyst exhibited high catalytic activity and selectivity towards the A3 -coupling reaction involving benzaldehyde, diethylamine, and phenylacetylene.
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We report the synthesis and structure of tertiary chiral nanostructures with 100 % optical purity. A novel synthetic strategy, using chiral reducing agent, R and S-BINAPCuBH4 (BINAP is 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl), is developed to access to atomically precise, intrinsically chiral [Au7 Ag6 Cu2 (R- or S-BINAP)3 (SCH2 Ph)6 ]SbF6 nanoclusters in one-pot synthesis. The clusters represent the first tri-metallic superatoms with inherent chirality and fair stability. Both metal distribution (primary) and ligand arrangement (secondary) of the enantiomers exhibited perfect mirror images, and unprecedentedly, the self-assembly driven by the C-Hâ â â F interaction between the phenyl groups of the superatom moieties and SbF6 - anions induced the formation of bio-mimic left- and right-handed helices, achieving the tertiary chiral nanostructures. DFT calculations revealed the connections between the molecular details and chiral optical activity.
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Although atomically precise metalloid nanoclusters (NCs) of identical size with distinctly different molecular structures are highly desirable to understand the structural effects on the optical and photophysical properties, their synthesis remains highly challenging. Herein, we employed phosphine and thiol capping ligands featuring appropriate steric effects and synthesized a charge-neutral Ag NC with the formula Ag44 (EBT)26 (TPP)4 (EBT: 2-ethylbenzenethiolate; TPP: triphenylphosphine). The single-crystal X-ray structure reveals that this NC has a hollow metal core of Ag12 @Ag20 and a metal-ligand shell of Ag12 (EBT)26 (TPP)4 . The presence of mixed ligands and long V-shaped metal-ligand motifs on this NC has resulted in an enhancement of the NIR-II photoluminescence quantum yield by >25-fold compared to an all-thiolate-stabilized anionic [Ag44 (SR)30 ]4- NC (SR: thiolate). Time-dependent density-functional calculations show that our Ag44 NC is an 18-electron superatom with a modulated electronic structure as compared to the [Ag44 (SR)30 ]4- anion, significantly influencing its optical properties.
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Deciphering the molecular pictures of the multi-component and non-periodic organic-inorganic interlayer is a grand technical challenge. Here we show that the atomic arrangement of hybrid surface ligands on metal nanoparticles can be precisely quantified through comprehensive characterization of a novel gold cluster, Au44 (i Pr2 -bimy)9 (PA)6 Br8 (1), which features three types of ligands, namely, carbene (1,3-diisopropylbenzimidazolin-2-ylidene, i Pr2 -bimy), alkynyl (phenylacetylide, PA), and halide (Br), respectively. The delicately balanced stereochemical effects and bonding capabilities of the three ligands give rise to peculiar geometrical and electronic structures. Remarkably, despite its complex and highly distorted surface structure, cluster 1 exhibits unusual catalytic properties and yet it is highly stable, both chemically and thermally. Moreover, rich reactive sites on the cluster surface raise the prospect of bio-compatibility (as it can be functionalized to yield water-soluble derivatives) and bio-applications.
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Atomically precise coinage metal (Au, Ag, and Cu) nanoclusters (NCs) have been the subject of immense interest for their intriguing structural, photophysical, and catalytic properties. However, the synthesis of Cu NCs is highly challenging because of low reduction potential and high reactivity of copper, demonstrating the need for new synthetic methods using appropriate ligand combinations. By designing a diamine-assisted synthetic strategy, here we report the synthesis and total structure characterization of a box-like dianionic Cu NC [Cu32(PET)24H8Cl2](PPh4)2 coprotected by 2-phenylethanethiolate (PET), hydride, and chloride ligands. Its crystal structure comprises a rare bisquare antiprismatic Cu14H8 core, assembled by two square antiprisms by edge sharing, followed by hydride binding. The rod-shaped Cu14H8 core is clamped by two complex Cu7(PET)11Cl and two simple Cu2PET metal ligand frameworks, constructing the complete structure of Cu32 NC. The presence, number, and location of hydrides are established by combined experimental and density functional theory results. The electronic structure calculations show the cluster as a zero-free-electron system, reproduce well the measured optical absorption spectrum, and explain the main absorption features. Furthermore, the Cu32 cluster is found to be a highly active homogeneous catalyst for C-N bond formation in aniline carbonylation reactions at room temperature. We hope that new findings in this work will stimulate and expand the research on Cu and other active metal NCs.
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The conventional synthetic methodology for atomically precise gold nanoclusters by using reduction in solution offers only the thermodynamically most stable nanoclusters. Herein, a solubility-driven isolation strategy is reported to access a metastable gold cluster. The cluster, with the composition of [Au9 (PPh3 )8 ]+ (1), displays an unusual, nearly perfect body-centered cubic (bcc) structure. As revealed by ESI-MS and UV/Vis measurements, the cluster is metastable in solution and converts to the well-known [Au11 (PPh3 )8 Cl2 ]+ (2) within just 90â min. DFT calculations revealed that although both 1 and 2 are eight-electron superatoms, there is a driving force to convert 1 to 2 as shown by the increased cohesion and larger HOMO-LUMO energy gap of 2. The isolation and crystallization of the metastable gold cluster were achieved in a biphasic reaction system in which reduction of gold precursors and crystallization of 1 took place concurrently. This synthetic protocol represents a successful strategy for investigations of other metastable species in metal nanocluster chemistry.