Dataset Information

Gas-phase fragmentation of single heteroatom-incorporated Co₅MS₈(PEt₃)₆⁺ (M = Mn, Fe, Co, Ni) nanoclusters.

ABSTRACT: Functionalization of metal-chalcogenide clusters by either replacing core atoms or by tuning the ligand is a powerful technique to tailor their properties. Central to this approach is understanding the competition between the strength of the metal-ligand and metal-metal interactions. Here, using collision-induced dissociation of atomically precise metal sulfide nanoclusters, Co₅MS₈L₆⁺ (L = PEt₃, M = Mn, Fe, Co, Ni) and Co_5-xFe_xS₈L₆⁺ (x = 1-3), we study the effect of a heteroatom incorporation on the core-ligand interactions and relative stability towards fragmentation. Sequential ligand loss is the dominant dissociation pathway that competes with ligand sulfide (LS) loss. Because the ligands are attached to metal atoms, LS loss is an unusual dissociation pathway, indicating significant rearrangement of the core prior to fragmentation. Both experiments and theoretical calculations indicate the reduced stability of Co₅MnS₈L₆⁺ and Co₅FeS₈L₆⁺ towards the first ligand loss in comparison with their Co₆S₈L₆⁺ and Co₅NiS₈L₆⁺ counterparts and provide insights into the core-ligand interaction.

SUBMITTER: Gholipour-Ranjbar H

PROVIDER: S-EPMC9814561 | biostudies-literature | 2022 Oct

REPOSITORIES: biostudies-literature

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Gas-phase fragmentation of single heteroatom-incorporated Co5MS8(PEt3)6+ (M = Mn, Fe, Co, Ni) nanoclusters.

Gholipour-Ranjbar Habib H Deepika Jena Puru P Laskin Julia J

Communications chemistry 20221019 1

Functionalization of metal-chalcogenide clusters by either replacing core atoms or by tuning the ligand is a powerful technique to tailor their properties. Central to this approach is understanding the competition between the strength of the metal-ligand and metal-metal interactions. Here, using collision-induced dissociation of atomically precise metal sulfide nanoclusters, Co5MS8L6+ (L = PEt3, M = Mn, Fe, Co, Ni) and Co5-xFe<sub ...[more]

PMID: 36697963

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Project description:A theoretical study of geometrical structures, electronic properties, and spectral properties of single-atom transition metal-doped boron clusters MB24 - (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) is performed using the CALYPSO approach for the global minimum search, followed by density functional theory calculations. The global minima obtained for the MB24 - (M = Sc, Ti, V, and Cr) clusters correspond to cage structures, and the MB24 - (M = Mn, Fe, and Co) clusters have similar distorted four-ring tubes with six boron atoms each. Interestingly, the global minima obtained for the NiB24 - cluster tend to a quasi-planar structure. Charge population analyses and valence electron density analyses reveal that almost one electron on the transition-metal atoms transfers to the boron atoms. The electron localization function (ELF) of MB24 - (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) indicates that the local delocalization of MB24 - (M = Sc, Ti, V, Cr, and Ni) is weaker than that of MB24 - (M = Mn, Fe, and Co), and there is no obvious covalent bond between doped metal and B atoms. The spin density and spin population analyses reveal that open-shell MB24 - (M = Ti, Cr, Fe, and Ni) has different spin characteristics which are expected to lead to interesting magnetic properties and potential applications in molecular devices. The polarizability of MB24 - (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) shows that MB24 - (M = Mn, Fe, and Co) has larger first hyperpolarizability, indicating that MB24 - (M = Mn, Fe, and Co) has a strong nonlinear optical response. Hence, MB24 - (M = Mn, Fe, and Co) might be considered as a promising nonlinear optical boron-based nanomaterial. The calculated spectra indicate that MB24 - (M = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) has different and meaningful characteristic peaks that can be compared with future experimental values and provide a theoretical basis for the identification and confirmation of these single-atom transition metal-doped boron clusters. Our work enriches the database of geometrical structures of doped boron clusters and can provide an insight into new doped boron clusters.

Dataset Information

Gas-phase fragmentation of single heteroatom-incorporated Co₅MS₈(PEt₃)₆⁺ (M = Mn, Fe, Co, Ni) nanoclusters.

Publications

Gas-phase fragmentation of single heteroatom-incorporated Co<sub>5</sub>MS<sub>8</sub>(PEt<sub>3</sub>)<sub>6</sub><sup>+</sup> (M = Mn, Fe, Co, Ni) nanoclusters.

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