Motif-to-Core Nucleation in a Decahedral Evolution Pattern.

Area of Science:

• Nanomaterials Science
• Inorganic Chemistry
• Computational Chemistry

Background:

• Ultrasmall metal nanoclusters offer atomic precision for studying nanomaterial evolution.
• Understanding structural principles at the molecular level is crucial for nanomaterial design.

Purpose of the Study:

• To report a novel series of super-atomic silver (Ag) clusters with distinct core structures.
• To investigate the structural correlation between Ag atoms in AgS2 blocks and cluster cores.
• To elucidate the motif-to-core evolution in the formation of these Ag nanoclusters.

Main Methods:

• Synthesis and characterization of four novel silver nanoclusters: [Ag19(TBBT)16(DPPP)4]+ (Ag19), [Ag22(DMAT)8(DPPM)4Cl8]2+ (Ag22), Ag26(SPh3,5-CF3)15(DPPF)4Cl5 (Ag26), and [Ag30(DMAT)12(DPPP)4Cl8]2+ (Ag30).
• Analysis of core structures, identifying decahedral Ag7, perpendicular bi-decahedrons, 3D penta-decahedrons, and hexa-decahedrons.
• Density functional theory (DFT) calculations to determine electronic configurations and super-atomic character.

Main Results:

• The study identified four novel super-atomic silver clusters (Ag19, Ag22, Ag26, Ag30) with distinct core architectures.
• A strong structural correlation was observed between Ag atoms in AgS2 blocks and the decahedral cores, indicating a motif-to-core evolution.
• DFT calculations confirmed excellent super-atomic characters for these clusters, corresponding to 1S2, 1S21P2, 1S21P4, and 1S21P6 electron configurations.

Conclusions:

• The findings demonstrate a clear motif-to-core evolution pathway in the self-assembly of silver nanoclusters.
• The identified silver clusters exhibit remarkable super-atomic electronic properties, validating theoretical predictions.
• This work provides fundamental insights into the structural principles governing metal nanomaterials at the atomic scale.