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Surface modifications of eight-electron palladium silver superatomic alloys.

ABSTRACT: Atomically precise thiolate-protected coinage metal nanoclusters and their alloys are far more numerous than their selenium congeners, the synthesis of which remains extremely challenging. Herein, we report the synthesis of a series of atomically defined dithiophosph(in)ate protected eight-electron superatomic palladium silver nanoalloys [PdAg₂₀{S₂PR₂}₁₂], 2a-c (where R = OⁱPr, a; OⁱBu, b; Ph, c) via ligand exchange and/or co-reduction methods. The ligand exchange reaction on [PdAg₂₀{S₂P(OⁿPr)₂}₁₂], 1, with [NH₄{Se₂PR₂}₁₂] (where R = OⁱPr, or OⁿPr) leads to the formation of [PdAg₂₀{Se₂P(OⁱPr)₂}₁₂] (3) and [PdAg₂₀{Se₂P(OⁿPr)₂}₁₂] (4), respectively. Solid state structures of 2a, 2b, 3 and 4 unravel different PdAg₂₀ metal frameworks from their parent cluster, originating from the different distributions of the eight-capping silver(I) atoms around a Pd@Ag₁₂ centered icosahedron with C_2, D_3, T_h and T_h symmetries, respectively. Surprisingly ambient temperature crystallization of the reaction product 3 obtained by the ligand exchange reaction on 1 has resulted in the co-crystallization of two isomers in the unit cell with overall T (3a) and C₃ (3b) symmetries, respectively. To our knowledge, this is the first ever characterized isomeric pair among the selenolate-protected NCs. Density functional theory (DFT) studies further rationalize the preferred geometrical isomerism of the PdAg₂₀ core.

SUBMITTER: Barik SK

PROVIDER: S-EPMC9814913 | biostudies-literature | 2022 Nov

REPOSITORIES: biostudies-literature

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Surface modifications of eight-electron palladium silver superatomic alloys.

Barik Subrat Kumar SK Chen Chih-Yuan CY Chiu Tzu-Hao TH Ni Yu-Rong YR Gam Franck F Chantrenne Isaac I Kahlal Samia S Saillard Jean-Yves JY Liu C W CW

Communications chemistry 20221119 1

Atomically precise thiolate-protected coinage metal nanoclusters and their alloys are far more numerous than their selenium congeners, the synthesis of which remains extremely challenging. Herein, we report the synthesis of a series of atomically defined dithiophosph(in)ate protected eight-electron superatomic palladium silver nanoalloys [PdAg20{S2PR2}12], 2a-c (where R = OiPr, a; OiBu, b; Ph, c) via ligand exchange and/or co-redu ...[more]

PMID: 36697889

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Project description:In this work, two kinds of competition between different Heusler structure types are considered, one is the competition between XA and L21 structures based on the cubic system of full-Heusler alloys, Pd2 YZ (Y = Co, Fe, Mn; Z = B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, P, As, Sb). Most alloys prefer the L21 structure; that is, Pd atoms tend to occupy the a (0, 0, 0) and c (0.5, 0.5, 0.5) Wyckoff sites, the Y atom is generally located at site b (0.25, 0.25, 0.25), and the main group element Z has a preference for site d (0.75, 0.75, 0.75), meeting the well known site-preference rule. The difference between these two cubic structures in terms of their magnetic and electronic properties is illustrated further by their phonon dispersion and density-of-states curves. The second type of competition that was subjected to systematic study was the competitive mechanism between the L21 cubic system and its L10 tetragonal system. A series of potential tetragonal distortions in cubic full-Heusler alloys (Pd2 YZ) have been predicted in this work. The valley-and-peak structure at, or in the vicinity of, the Fermi level in both spin channels is mainly attributed to the tetragonal ground states according to the density-of-states analysis. ΔE M is defined as the difference between the most stable energy values of the cubic and tetragonal states; the larger the value, the easier the occurrence of tetragonal distortion, and the corresponding tetragonal structure is stable. Compared with the ΔE M values of classic Mn2-based tetragonal Heusler alloys, the ΔE M values of most Pd2CoZ alloys in this study indicate that they can overcome the energy barriers between cubic and tetragonal states, and possess possible tetragonal transformations. The uniform strain has also been taken into consideration to further investigate the tetragonal distortion of these alloys in detail. This work aims to provide guidance for researchers to further explore and study new magnetic functional tetragonal materials among the full-Heusler alloys.

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Surface modifications of eight-electron palladium silver superatomic alloys.

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Surface modifications of eight-electron palladium silver superatomic alloys.

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