Designed construction of two new atom-precise three-dimensional and two-dimensional Ag₁₂ cluster-assembled materials

Area of Science:

• Materials Science
• Nanotechnology
• Crystallography

Background:

• Silver cluster-assembled materials (SCAMs) are crystalline extended materials with precise structures and tunable functions.
• Understanding the relationship between discrete nanoclusters and their assembled structures is crucial for materials design.

Purpose of the Study:

• To report the first synthesis of a 3D SCAM using Ag12 cluster nodes and a tritopic linker (TPMA).
• To prepare a 2D SCAM using Ag12 cluster nodes and a different tritopic linker (TPEB).
• To elucidate the atomic-level transformation of silver nanocluster symmetry upon assembly into extended SCAMs.

Main Methods:

• Synthesis of silver cluster-assembled materials (SCAMs) using Ag12 nodes and tritopic organic linkers (TPMA and TPEB).
• Characterization using microscopic and diffraction analyses to determine morphology, structural robustness, and phase purity.
• Analysis of the impact of organic linker binding on the symmetry of silver nanoclusters (NCs).

Main Results:

• Successful synthesis of a novel (3,6)-connected 3D SCAM, [Ag12(S^tBu)6(CF3COO)6(TPMA)6] (TUS 6).
• Preparation of a novel 2D SCAM, [Ag12(S^tBu)6(CF3COO)6(TPEB)6] (TUS 7).
• Demonstration of distinct morphologies, structural robustness, and phase purity for both synthesized SCAMs.
• Detailed explanation of how organic linkers alter nanocluster symmetry during the assembly process.

Conclusions:

• This study presents the first atomic-level understanding of symmetry transformation from discrete silver nanoclusters to extended SCAM structures.
• The findings provide insights into the design principles for novel SCAMs with tailored properties.
• The work opens new avenues for exploring structure-property relationships in cluster-based materials.