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

Riki Nakatani; Jin Sakai; Aishik Saha; Ayumu Kondo; Rina Tomioka; Tokuhisa Kawawaki; Saikat Das; Yuichi Negishi

doi:10.1039/d4nr03992k

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

Nanoscale. 2024 Nov 25. doi: 10.1039/d4nr03992k. Online ahead of print.

Authors

Riki Nakatani¹, Jin Sakai¹, Aishik Saha², Ayumu Kondo¹, Rina Tomioka¹, Tokuhisa Kawawaki¹, Saikat Das¹, Yuichi Negishi^{1

3}

Affiliations

¹ Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan. saikatdas@rs.tus.ac.jp.
² Department of Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai 400 076, India.
³ Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan. yuichi.negishi.a8@tohoku.ac.jp.

PMID: 39585368
DOI: 10.1039/d4nr03992k

Abstract

Silver cluster-assembled materials (SCAMs) are well-defined crystalline extended materials hallmarked by their unique geometric structures, atomically precise designability and functional modularity. In this study, we report for the first time the synthesis of a (3,6)-connected three-dimensional (3D) SCAM, [Ag₁₂(S^tBu)₆(CF₃COO)₆(TPMA)₆]_n (designated as TUS 6), TPMA = tris(pyridine-4-ylmethyl)amine, by assembling Ag₁₂ cluster nodes with the help of a tritopic linker TPMA. Besides, we also prepared a two-dimensional (2D) SCAM, [Ag₁₂(S^tBu)₆(CF₃COO)₆(TPEB)₆]_n (described as TUS 7), TPEB = 1,3,5-tris(pyridine-4-ylethynyl)benzene, by reticulating Ag₁₂ nodes with a tritopic linker TPEB. Characterized by microscopic and diffraction analyses, the SCAMs revealed distinct morphologies, structural robustness, and phase purity. This paper elucidates how the binding with the organic linkers alters the symmetry of the silver nanoclusters (NCs). Changes in the symmetry of discrete NCs to assembled structures have not been reported yet. This study provides an atomic-level explanation of the transformation of symmetry from NCs to extended structures.