異方的成長による量子ニードルの合成を実現～近赤外光応答ナノ物質の開発に向けて～

2025-09-05 東京大学

金ナノクラスターの異方的な逐次成長

＜関連情報＞

• https://www.s.u-tokyo.ac.jp/ja/press/10899/
• https://pubs.acs.org/doi/10.1021/jacs.5c11089

チオレート保護金クラスターにおける核生成と異方性成長のX線結晶構造解析：金量子針の標的合成に向けて X-ray Crystallographic Visualization of a Nucleation and Anisotropic Growth in Thiolate-Protected Gold Clusters: Toward Targeted Synthesis of Gold Quantum Needles

Shinjiro Takano,Yuya Hamasaki,Tatsuya Tsukuda
Journal of the American Chemical Society  Published: September 4, 2025
DOI:https://doi.org/10.1021/jacs.5c11089

Abstract

Understanding and controlling the nucleation and growth processes of gold clusters are crucial for advancing the nucleation theory and targeted cluster synthesis. While in situ mass spectrometry has revealed the intermediate species formed during the growth process, the overall structural evolution remains unclear due to a lack of crystallographic information. In this study, we examined a new synthetic method for thiolate-protected gold clusters in their embryonic stage. In this method, only partial Au(I) precursors are reduced by a minimal amount of mild reductant in the presence of a substoichiometric amount of thiol. Under optimized conditions, we obtained a series of small gold clusters, including Au₁₅(SCTMS)₁₃, Au₁₈(SCTMS)₁₄, Au₂₂(SCTMS)₁₈, Au₂₃(SCTMS)₁₇, Au₂₅(SCTMS)₁₈, Au₃₃(SCTMS)₂₅, and Au₃₄(SCTMS)₂₆ (TMSCS^–: trimethylsilylmethanethiolate), and successfully determined their geometric structures via single-crystal X-ray diffraction analysis. Unexpectedly, the synthetic yield of Au₂₅(SCTMS)₁₈ with an icosahedral Au₁₃ core was very low despite the stability of this composition. The obtained structural information suggests that under our synthetic conditions the dominant process is the assembly of triangular Au₃ and tetrahedral Au₄ units, each with two electrons, in an anisotropic structure followed by passivation with unreduced Au(I)-SCTMS complexes. Notably, Au₃₃(SCTMS)₂₅ and Au₃₄(SCTMS)₂₆ have a pencil-shaped Au₁₆ core with an Au₃ width and exhibit strong absorption and emission in the near-infrared region. Due to their extremely thin diameter and quantized electronic structures, we propose naming these anisotropic species “gold quantum needles”. This study deepens our understanding of the cluster formation mechanism at the atomic level and provides a novel synthetic route for highly anisotropic gold clusters.