Search results for "Nanoclusters"
showing 10 items of 164 documents
Atomically Precise Alkynyl- and Halide-Protected AuAg Nanoclusters Au78Ag66(C≡CPh)48Cl8 and Au74Ag60(C≡CPh)40Br12: The Ligation Effects of Halides
2021
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-s...
Jahn–Teller effects in Au25(SR)18
2016
The relationship between oxidation state, structure, and magnetism in many molecules is well described by first-order Jahn–Teller distortions. This relationship is not yet well defined for ligated nanoclusters and nanoparticles, especially the nano-technologically relevant gold-thiolate protected metal clusters. Here we interrogate the relationships between structure, magnetism, and oxidation state for the three stable oxidation states, 1, 0 and +1 of the thiolate protected nanocluster Au25(SR)18. We present the single crystal X-ray structures of the previously undetermined charge state Au25(SR)18+1, as well as a higher quality single crystal structure of the neutral compound Au25(SR)180 . …
CO Oxidation on Cationic Gold Clusters: A Theoretical Study
2008
Aiming at understanding the elementary steps governing the oxidation of CO catalyzed by dispersed or supported gold nanoclusters, the reactivity of molecular species, such as O2 and CO, on neutral and positively charged Au13 clusters have been studied using a DFT approach. Two CO oxidation mechanisms have been simulated, involving respectively the adsorption of CO and O2 on adjacent catalytic sites (two-sites mechanism) and the competitive interaction of the reactants on the same site (single-site mechanism). It is demonstrated that in the former scheme a definite interaction of CO and O2 with both the charged and neutral cluster is effective, but that a chemical reaction between the adsorb…
Robust, Highly Luminescent Au13 Superatoms Protected by N-Heterocyclic Carbenes
2019
Gold superatom nanoclusters stabilized entirely by N-heterocyclic carbenes (NHCs) and halides are reported. The reduction of well-defined NHC–Au–Cl complexes produces clusters comprised of an icosahedral Au13 core surrounded by a symmetrical arrangement of nine NHCs and three chlorides. X-ray crystallography shows that the clusters are characterized by multiple CH−π and π–π interactions, which rigidify the ligand and likely contribute to the exceptionally high photoluminescent quantum yields observed, up to 16.0%, which is significantly greater than that of the most luminescent ligand-protected Au13 superatom cluster. Density functional theory analysis suggests that clusters are 8-electron …
Surface Chemistry Controls Magnetism in Cobalt Nanoclusters
2016
Magnetic properties of Co13 and Co55 nanoclusters, passivated by surface ligand shells that exhibit varying electronic interactions with the metal, are studied using density functional theory. The calculations show that the chemical nature of the bond between the ligand and the metal core (X-type or L-type) impacts the total magnetic moment of Co nanoclusters dramatically. Furthermore, the chemical identity of the ligand within each binding motif then provides a fine handle on the exhibited magnetic moment of the cluster. Thus, ligand shell chemistry is predicted to not only stabilize Co nanoclusters, but provide a powerful approach to control their magnetic properties, which combined enabl…
Cubic aromaticity in ligand-stabilized doped Au superatoms
2021
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 arom…
Support work function as a descriptor and predictor for the charge and morphology of deposited Au nanoparticles.
2020
We show, using density functional theory calculations, that the charge, magnetic moment, and morphology of deposited Au nanoclusters can be tuned widely by doping the oxide support with aliovalent cations and anions. As model systems, we have considered Aun (n = 1, 2, or 20) deposited on doped MgO and MgO/Mo supports. The supports have been substitutionally doped with varying concentrations θ of F, Al, N, Na, or Li. At θ = 2.78%, by varying the dopant species, we are able to tune the charge of the Au monomer between −0.84e and +0.21e, the Au dimer between −0.87e and −0.16e, and, most interestingly, Au20 between −3.97e and +0.49e. These ranges can be further extended by varying θ. These chan…
Highly Robust but Surface‐Active: An N‐Heterocyclic Carbene‐Stabilized Au 25 Nanocluster
2019
Surface organic ligands play a critical role in stabilizing atomically precise metal nanoclusters in solutions. However, it is still challenging to prepare highly robust ligated metal nanoclusters that are surface-active for liquid-phase catalysis without any pre-treatment. Now, an N-heterocyclic carbene-stabilized Au25 nanocluster with high thermal and air stabilities is presented as a homogenous catalyst for cycloisomerization of alkynyl amines to indoles. The nanocluster, characterized as [Au25 (i Pr2 -bimy)10 Br7 ]2+ (i Pr2 -bimy=1,3-diisopropylbenzimidazolin-2-ylidene) (1), was synthesized by direct reduction of AuSMe2 Cl and i Pr2 -bimyAuBr with NaBH4 in one pot. X-ray crystallization…
Globally Optimized Equilibrium Shapes of Zirconia-Supported Rh and Pt Nanoclusters: Insights into Site Assembly and Reactivity
2019
Metal–support interfaces form an active site for many important catalytic reactions. The modeling of these interfacial sites calls for approximations to set up a structure model, which in turn may ...
BiI3 nanoclusters in melt-grown CdI2 crystals studied by optical absorption spectroscopy
2013
Optical absorption spectroscopy of CdI2–BiI3 layered crystals has been performed in the temperature range of 77–300 K. The main absorption, observed in these crystals at 2.59 eV is related to quantum confined exciton absorption of bimolecular BiI3 cluster. Low energy absorption peaks at 2.38 eV, 2.06 eV and 1.94 eV can be tentatively assigned to larger clusters composed of 4, 6 or more BiI3 molecules. In ultra-thin samples of CdI2–BiI3 several bands at 2.84 eV, 3.03 eV and 3.27 eV were observed which are ascribed to higher excited states of the excitons in bimolecular BiI3 cluster.