Kamiyama Maho, Shingyouchi Yamato, Sarma Rupa, Ghosh Mandira, Kawawaki Tokuhisa, Biswas Sourav, Negishi Yuichi
Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
Research Institute for Science & Technology, Tokyo University of Science, Tokyo 162-8601, Japan.
Chem Commun (Camb). 2025 Jan 14;61(6):1048-1062. doi: 10.1039/d4cc06139j.
Research on copper nanoclusters (Cu NCs) is expanding rapidly due to their remarkable structural versatility and related tunable properties they exhibit. This fast-paced development creates a need for a comprehensive overview of the structural evolution of Cu NCs, especially regarding how different geometric configurations emerge from variations in the ligand choice. In light of this, this feature article focuses on the role of thiolate ligands in shaping the structural and electronic properties of Cu NCs, with a particular emphasis on how modifications of ligands influence the geometry of NCs. While thiolates play a central role in stabilizing Cu NCs, this feature article also underscores the significance of co-ligands-such as hydrides, phosphines, and halides-because relying solely on thiolates is often insufficient to fully protect the surface of Cu NCs, unlike in the case of gold or silver NCs. A detailed analysis of how various thiolates and co-ligands affect core geometry reveals a direct correlation with the electronic properties of Cu NCs, which in turn influences their optical behavior. By examining these ligand-driven structural and electronic changes, this feature article aims to provide a deeper understanding of the relationship between ligand design and the resulting NC properties. The ultimate goal is to offer a strategy for the rational design of Cu NCs with tailored functionalities, thereby advancing NC chemistry and opening up new possibilities for applications in optoelectronics, catalysis, and sensing.
由于铜纳米团簇（Cu NCs）具有显著的结构多样性以及由此展现出的可调谐性质，对其研究正在迅速扩展。这种快速发展使得有必要对Cu NCs的结构演变进行全面概述，特别是关于不同几何构型如何因配体选择的变化而出现。鉴于此，这篇专题文章聚焦于硫醇盐配体在塑造Cu NCs的结构和电子性质方面的作用，特别强调配体的修饰如何影响纳米团簇的几何形状。虽然硫醇盐在稳定Cu NCs方面起着核心作用，但这篇专题文章也强调了共配体（如氢化物、膦和卤化物）的重要性，因为与金或银纳米团簇的情况不同，仅依靠硫醇盐往往不足以完全保护Cu NCs的表面。对各种硫醇盐和共配体如何影响核心几何形状的详细分析揭示了与Cu NCs电子性质的直接关联，这反过来又影响它们的光学行为。通过研究这些由配体驱动的结构和电子变化，这篇专题文章旨在更深入地理解配体设计与所得纳米团簇性质之间的关系。最终目标是提供一种策略，用于合理设计具有定制功能的Cu NCs，从而推动纳米团簇化学发展，并为光电子学、催化和传感领域的应用开辟新的可能性。
