Co13O8—metalloxocubes: a new class of perovskite-like neutral clusters with cubic aromaticity

Geng, Lijun; Weng, Mouyi; Xu, Chaoqun; Zhang, Hanyu; Cui, Chaonan; Wu, Haiming; Chen, Xin; Hu, Mingyu; Lin, Hai; Sun, Zhen‐Dong; Wang, Xi; Hu, Han‐Shi; Li, Jun; Zheng, Jiaxin; Luo, Zundu; Pan, Feng; Yao, Jiannian

doi:10.1093/nsr/nwaa201

Cited by 25 publications

(18 citation statements)

References 57 publications

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“…− and Pt 10 − , respectively, but there is a lack of − unit) are fully occupied while the antibonding 6sbased MOs are vacant, corresponding to three-dimensional allmetal aromaticity, 34,36 with n = 1 at a configuration of (33e 1 ) 2 (34e 1 ) 2 (21b 2 ) 2 (22a 1 ) 2 , which is also consistent with the PDOS analysis (Figure S18). The orbital interaction analysis is coincident with the four 10c−2e delocalized bonds given by AdNDP analysis (Figure 6).…”

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confidence: 99%

Tetrahedral Pt₁₀^– Cluster with Unique Beta Aromaticity and Superatomic Feature in Mimicking Methane

Jia

Zhang

et al. 2021

J. Phys. Chem. Lett.

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Utilizing a customized metal cluster source in tandem with a flow tube reactor and a reflectron time-of-flight mass spectrometer, we have obtained well-resolved pure metal clusters Pt n − and observed their gas-phase reactions with a few small gas molecules. Interestingly, the remarkable inertness of Pt 10 − was repeatedly observed in different reactions. Meanwhile, we have determined the structure of Pt 10 − within a regular tetrahedron. Considering that Pt possesses 5d 9 6s 1 electron configuration, the tetrahedral Pt 10 − exhibits unexpected stability at neither a magic number of valence electrons nor a shell closure of geometric structure. Comprehensive theoretical calculations unveil the stability of Pt 10 − is significantly associated with the allmetal aromaticity. In addition to the classical total aromaticity, which is mainly due to 6s electrons, there is unique beta-aromaticity ascribed to spin-polarized beta 5d electrons pertaining to singly occupied multicenter bonds. Further, we demonstrate the superatomic feature of such a transition metal cluster Pt 10 − , as Pt 6 @Pt 4 − , in mimicking methane.

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confidence: 99%

Tetrahedral Pt₁₀^– Cluster with Unique Beta Aromaticity and Superatomic Feature in Mimicking Methane

Jia

Zhang

et al. 2021

J. Phys. Chem. Lett.

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“…29 Inspite of these interesting results, since the transition metals (IIIB−XB) readily form coordination and oxidation products, it remains a big challenge to prepare pure metal clusters and to determine magic numbers directly by observing their mass abundances in gas-phase reactions. Recently, we have successfully produced "metalloxocubes" by the reaction of cobalt clusters with oxygen, 41 which is identified as a stable oxygen-passivated metal cluster, 42 and can be classified into the general category of the superatom family. In another work, we studied the reactions of Co n ±/0 clusters with ammonia; the dehydrogenation from ammonia with both dramatic charge-and size-dependent reactivities has been observed.…”

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confidence: 99%

Reactivity of Cobalt Clusters Co_n^±/0 with Dinitrogen: Superatom Co₆⁺ and Superatomic Complex Co₅N₆⁺

et al. 2021

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We report a joint experimental and theoretical study on the reactions of cobalt clusters (Co n ±/0 ) with nitrogen using the customized reflection time-of-flight mass spectrometer combined with a 177.3 nm deepultraviolet laser. Comparing to the behaviors of neutral Co n (n = 2−30) and anionic Co n − clusters (n = 7−53) which are relatively inert in reacting with nitrogen in the fast-flow tube, Co n + clusters readily react with nitrogen resulting in adducts of one or multiple N 2 except Co 6 + which stands firm in the reaction with nitrogen. Detailed quantum chemistry calculations, including the energetics, electron occupancy, and orbital analysis, wellexplained the reasonable reactivity of Co n + clusters with nitrogen and unveiled the open-shell superatomic stability of Co 6 + within a highly symmetric (D 3d ) structure. The D 3d Co 6+ bears an electron configuration of a half-filled superatomic 1P orbital (i.e., 1S 2 1P 3 ||1D 0 ), a large α-highest occupied molecular orbital (HOMO)−lowest unoccupied molecular orbital (LUMO) gap, symmetric multicenter bonds, and reasonable electron delocalization pertaining to metallic aromaticity. Topology analysis by atom-in-molecule illustrates the interactions between Co n + and N 2 corresponding to covalent bonds, but the Co−N interactions in cationic Co 2 + N 2 and Co 6 + N 2 clusters are apparently weaker than those in the other systems. In addition, we identify a superatomic complex Co 5 N 6 + which exhibits similar frontier orbitals as the naked Co 5 + cluster, but the alpha HOMO−LUMO gap is nearly double-magnified, which is consistent with the high-abundance peak of Co 5 N 6 + in the experimental observation. The enhanced stability of such a ligand-coordinated superatomic complex Co 5 N 6 + , along with the superatom Co 6 + with aromaticity, sheds light on special and general superatoms.

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“…Recently, we have developed an integrated instrument of reflection a time-of-flight mass spectrometer (Re-TOFMS) with an ultrafast deep-ultraviolet (DUV) laser for photoionization. The DUV laser (177.3 nm) has a short pulse duration (15 ps) and appropriate pulse energy (∼20 μJ), − which happens to be applicable for highly efficient and low-fragment photoionization of the neutral vanadium clusters and their hydrates. Taking advantage of the DUV laser ionization and our experiences in preparing metal clusters, we have been able to observe the well-resolved mass distribution of neutral vanadium clusters V n ( n = 1–40), and here we have studied the gas-phase reactions with a few chemicals including N 2 , CO 2 , and D 2 O in the flow-tube reactor (the etching reaction with O 2 reported in the previous study).…”

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Vanadium Cluster Neutrals Reacting with Water: Superatomic Features and Hydrogen Evolution in a Fishing Mode

Zhang

Jia

et al. 2021

J. Phys. Chem. Lett.

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Hydrogen evolution reaction (HER) is known as the heart of various energy storage and conversation systems of renewable energy sources. Here we observe the cluster reactions of a light transition metal, vanadium, with water in a gas-phase flow tube reactor. While HER products of V1 and V2 were not observed, the effective HER of water on neutral V n (n ≥ 3) clusters reveals reasonable and size-dependent reactivity of the vanadium clusters. Superatomic features and reaction dynamics of V10, V13, and V16 are highlighted. Among the three typical superatoms, V10 and V16 exhibit an abnormal superatomic orbital energy level order, 1S|2S|1P|1D..., where the energy-reduced 2S orbital helps to accommodate the geometric structure and hence reinforce the cluster stability. In comparison, V13 bears a less symmetrical structure and reacts readily with water, allowing for recombination of a hydroxyl atom with an adsorbed hydrogen atom, akin to a fishing-mode HER process. The joint experimental and theoretical study on neutral V n clusters clarifies the availability of superatom chemistry for transition metals and appeals further development of cluster theory based on electronic cloud/orbital analysis instead of simply counting the valence electrons. Also, we provide insights into the HER mechanism of metal clusters and propose a strategy to design new materials for portable fuel cells of hydrogen energy.

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Co13O8—metalloxocubes: a new class of perovskite-like neutral clusters with cubic aromaticity

Cited by 25 publications

References 57 publications

Tetrahedral Pt₁₀^– Cluster with Unique Beta Aromaticity and Superatomic Feature in Mimicking Methane

Tetrahedral Pt₁₀^– Cluster with Unique Beta Aromaticity and Superatomic Feature in Mimicking Methane

Reactivity of Cobalt Clusters Co_n^±/0 with Dinitrogen: Superatom Co₆⁺ and Superatomic Complex Co₅N₆⁺

Vanadium Cluster Neutrals Reacting with Water: Superatomic Features and Hydrogen Evolution in a Fishing Mode

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Co13O8—metalloxocubes: a new class of perovskite-like neutral clusters with cubic aromaticity

Cited by 25 publications

References 57 publications

Tetrahedral Pt10– Cluster with Unique Beta Aromaticity and Superatomic Feature in Mimicking Methane

Tetrahedral Pt10– Cluster with Unique Beta Aromaticity and Superatomic Feature in Mimicking Methane

Reactivity of Cobalt Clusters Con±/0 with Dinitrogen: Superatom Co6+ and Superatomic Complex Co5N6+

Vanadium Cluster Neutrals Reacting with Water: Superatomic Features and Hydrogen Evolution in a Fishing Mode

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Tetrahedral Pt₁₀^– Cluster with Unique Beta Aromaticity and Superatomic Feature in Mimicking Methane

Tetrahedral Pt₁₀^– Cluster with Unique Beta Aromaticity and Superatomic Feature in Mimicking Methane

Reactivity of Cobalt Clusters Co_n^±/0 with Dinitrogen: Superatom Co₆⁺ and Superatomic Complex Co₅N₆⁺