Formation of Al
 +
 (C
 6
 H
 6
 )
 13
 : The Origin of Magic Number in Metal–Benzene Clusters Determined by the Nature of the Core

Zhang, Hanyu; Reber, Arthur C.; Geng, Lijun; Rabayda, Daniel; Wu, Haiming; Luo, Zundu; Yao, Jiannian

doi:10.31635/ccschem.019.20190033

Cited by 14 publications

(4 citation statements)

References 56 publications

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“…The experiments were conducted on a customized reflection time-of-flight mass spectrometer (Re-TOFMS) in combination with a laser evaporation (LaVa) source coupled with a fast-flow tube reactor. 30,31 A pulsed laser (532 nm, Nd 3+ :YAG, 15-20 mJ•pulse −1 , and 10 Hz) was used to generate the Ag n -(n = 10-34) clusters. The cluster ions generated in the gas channel were expanded and grown through a nozzle with an internal diameter of 1.5 mm, and then interacted with the reactant gas (O 2 seeded in He) in a compact fast-flow reactor (length ∼60 mm) with an instantaneous gas pressure at ∼55 Pa, that is, multiple collisions up to a few hundreds.…”

Section: Methodsmentioning

confidence: 99%

Superatomic Signature and Reactivity of Silver Clusters with Oxygen: Double Magic Ag ₁₇ ^– with Geometric and Electronic Shell Closure

Yin

Geng

et al. 2021

CCS Chem

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Understanding the stability and reactivity of silver clusters toward oxygen provides insights to design new materials of coinage metals with atomic precision. Herein, we report a systematic study on anionic silver clusters, Ag n − (n = 10-34), by reacting them with O 2 under multiple-collision conditions. Mass spectrometry observation presents the odd-even alternation effect on the reaction rates of these Ag n − clusters. A few chosen clusters such as Ag 13 − and Ag 17-19 − hold up in the presence of excessive oxygen gas reactants. First-principles calculation results reveal that the chemical stability of D 4d Ag 17 − is associated with its symmetric ellipsoidal structure and the electronic shell closure of superatomic orbitals (1S 2 | 1P 4 |1P 2 |1D 4 |1D 6 ||2S 0 ). This results in 17c-2e multicenter bonding and a large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap, the highest electron detachment energy and incremental binding energy among all the studied Ag n − clusters, as well as the smallest O 2 -binding energy and least charge transfer from Ag to O 2 . We fully demonstrate the superatomic signature of these silver clusters and emphasize the unique Ag 17 with both geometric and electronic shell closure, shedding light on the 18e stability for the coinage of metal clusters. The superatomic characteristics are also disclosed for Ag 16 − , Ag 18 − , and Ag 32 − clusters.

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Section: Methodsmentioning

confidence: 99%

Superatomic Signature and Reactivity of Silver Clusters with Oxygen: Double Magic Ag ₁₇ ^– with Geometric and Electronic Shell Closure

Yin

Geng

et al. 2021

CCS Chem

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“…The heavy oxygen isotope (oxygen-18) was used to clear the mass spectroscopic identification of water reaction products without interference of trace oxygen contamination (oxygen-16) in the vacuum chamber. A brief description of the apparatus is given here while detailed information can be found in our previously published studies 44 , 57 . The vanadium clusters (V n + ) were generated in the cluster formation channel after laser ablation of a vanadium disk (99.9% purity), with He (99.999%, 1.0 MPa backing pressure) as the buffer gas.…”

Section: Methodsmentioning

confidence: 99%

Hydrogen release from a single water molecule on Vn+ (3 ≤ n ≤ 30)

Zhang

Jia

et al. 2020

Commun Chem

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Water and its interactions with metals are closely bound up with human life, and the reactivity of metal clusters with water is of fundamental importance for the understanding of hydrogen generation. Here a prominent hydrogen evolution reaction (HER) of single water molecule on vanadium clusters Vn+ (3 ≤ n ≤ 30) is observed in the reaction of cationic vanadium clusters with water at room temperature. The combined experimental and theoretical studies reveal that the wagging vibrations of a V-OH group give rise to readily formed V-O-V intermediate states on Vn+ (n ≥ 3) clusters and allow the terminal hydrogen to interact with an adsorbed hydrogen atom, enabling hydrogen release. The presence of three metal atoms reduces the energy barrier of the rate-determining step, giving rise to an effective production of hydrogen from single water molecules. This mechanism differs from dissociative chemisorption of multiple water molecules on aluminium cluster anions, which usually proceeds by dissociative chemisorption of at least two water molecules at multiple surface sites followed by a recombination of the adsorbed hydrogen atoms.

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“…Optimized structures are also given at the PBE0/6-311+G(d,p) level of theory, which are consistent with previous studies. 27,55 Their stability is mainly attributed to the cation−π interactions between the Al n + and benzene molecules.…”

Section: ■ Experimental and Theoretical Methodsmentioning

confidence: 99%

“…While common features in the solvent structure around Al + and V + cations were revealed to be similar T-shaped benzene interactions, there are strikingly different patterns of the inner core due to the solvation number being 2 for the sandwiched vanadium complex while it is 3 or 4 for aluminum, giving rise to the prominent stability of V + Bz 2 and Al + Bz 13 , respectively. 27 These results offered a new window to understand the interactions and dynamics of nonpolar solvents around metal ions.…”

Section: ■ Introductionmentioning

confidence: 96%

Charge-Sensitive Cluster−π Interactions Cause Altered Reactivity of Al_n^±,0 Clusters with Benzene: Enhanced Stability of Al₁₃⁺Bz

et al. 2020

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Utilizing the homemade reflection time-of-flight mass spectrometer (Re-TOFMS), here we report a comprehensive study of the reactivity of aluminum clusters Al n ±,0 with molecular benzene in the gas-phase flow tube reactor. During the reactions with benzene, Al n + clusters were found to be relatively more reactive than Al n 0/–, and interestingly, the Al13 + cluster exhibited more reaction product than its neighboring Al n + clusters. With an emphasis on Al13 ±,0 clusters, we have performed an in-depth study utilizing DFT calculations to unravel the diverse reactivity of aluminum clusters with benzene. It is revealed that the Al13 +Bz cluster has a short Al–C distance and high binding energy, as well as an enlarged HOMO–LUMO gap in comparison with that of Al13 +. This contrasts with Al13 0/– and Al15 +, of which the HOMO–LUMO gaps are reduced when the cluster binds with a benzene molecule. Further, the cluster−π interactions between aluminum clusters and benzene are fully demonstrated via topological analysis, natural bonding orbital (NBO) analysis, and noncovalent interaction plots based on independent gradient model (IGM). The unique gyro-like structure of Al13 + and cluster−π interaction induce uneven redistribution of charges on the 13- atoms of Al13 +, enabling a tight Al–C bond with strong electrostatic attraction and orbital interactions, which largely differs from the weak orbital overlap and electrostatic repulsion between benzene molecule and Al13 0/– clusters.

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Formation of Al ⁺ (C ₆ H ₆ ) ₁₃ : The Origin of Magic Number in Metal–Benzene Clusters Determined by the Nature of the Core

Abstract: new details into coordination chemistry and a strategy to dissect the interactions of metal ions in solvents like benzene.

Cited by 14 publications

References 56 publications

Superatomic Signature and Reactivity of Silver Clusters with Oxygen: Double Magic Ag ₁₇ ^– with Geometric and Electronic Shell Closure

Superatomic Signature and Reactivity of Silver Clusters with Oxygen: Double Magic Ag ₁₇ ^– with Geometric and Electronic Shell Closure

Hydrogen release from a single water molecule on Vn+ (3 ≤ n ≤ 30)

Charge-Sensitive Cluster−π Interactions Cause Altered Reactivity of Al_n^±,0 Clusters with Benzene: Enhanced Stability of Al₁₃⁺Bz

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Formation of Al + (C 6 H 6 ) 13 : The Origin of Magic Number in Metal–Benzene Clusters Determined by the Nature of the Core

Abstract: new details into coordination chemistry and a strategy to dissect the interactions of metal ions in solvents like benzene.

Cited by 14 publications

References 56 publications

Superatomic Signature and Reactivity of Silver Clusters with Oxygen: Double Magic Ag 17 – with Geometric and Electronic Shell Closure

Superatomic Signature and Reactivity of Silver Clusters with Oxygen: Double Magic Ag 17 – with Geometric and Electronic Shell Closure

Hydrogen release from a single water molecule on Vn+ (3 ≤ n ≤ 30)

Charge-Sensitive Cluster−π Interactions Cause Altered Reactivity of Aln±,0 Clusters with Benzene: Enhanced Stability of Al13+Bz

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Formation of Al ⁺ (C ₆ H ₆ ) ₁₃ : The Origin of Magic Number in Metal–Benzene Clusters Determined by the Nature of the Core

Superatomic Signature and Reactivity of Silver Clusters with Oxygen: Double Magic Ag ₁₇ ^– with Geometric and Electronic Shell Closure

Superatomic Signature and Reactivity of Silver Clusters with Oxygen: Double Magic Ag ₁₇ ^– with Geometric and Electronic Shell Closure

Charge-Sensitive Cluster−π Interactions Cause Altered Reactivity of Al_n^±,0 Clusters with Benzene: Enhanced Stability of Al₁₃⁺Bz