山东大学孙頔团队报道了手性全二烷基保护超原子银纳米团簇的单原子“手术”。相关研究成果发表在2024年11月4日出版的《科学通报》。

纳米团簇金属核内单原子的操纵由于有可能在单原子水平上阐明基于核的结构-性质关系，引起了相当大的关注。

该文中，研究人员选择了新设计的手性双炔基配体作为保护剂，以分离两对8电子超原子银纳米簇R/S-Ag39和R/S-Ag40。X射线衍射分析表明，具有相同数量手性配体的Ag39和Ag40具有非常相似的银骨架，但只有一个原子差异。

与Ag39相比，将额外的Ag40原子掺入Ag40会引起结构和性质的两个显著变化：（i）整个纳米簇的对称性降低，导致与核相关的不对称g因子增强；（ii）调节激发态的跃迁（1P→1D和配体（π）→1D），导致第二次近红外（NIR-ii，1000-1700 nm）磷光发射红移从1088 nm到1150 nm。

该项工作不仅为单原子水平的结构和基态/激发态手性活动之间的关系，提供了重要的见解，而且还提出了双炔基，作为构建超原子金属纳米团簇的有前景的稳定剂。

附：英文原文

Title: Single-atom “surgery” on chiral all-dialkynyl-protected superatomic silver nanoclusters

Author: Di Sun a

Issue&Volume: 2024/11/04

Abstract: The manipulation of single atoms within the metallic kernel of nanoclusters has attracted considerable attention due to its potentials to elucidate kernel-based structure-property relationships at the single-atom level. Herein, new-designed chiral bialkynyl ligands, have been chosen as protective agents to isolate two pairs of 8-electron superatomic silver nanoclusters, R/S-Ag39 and R/S-Ag40. X-ray diffraction analysis reveals that Ag39 and Ag40 with the same number of chiral ligands, possess a closely analogous silver skeleton but a single-atomic difference. The incorporation of an extra Ag40th atom into Ag40 evokes two significant changes of structure and property compared to Ag39: (i) A reduction in the symmetry of the entire nanocluster, resulting in an enhancement of kernel-related asymmetry g-factor; (ii) a regulation of the transitions (1P → 1D and Ligand(π) → 1D) of excited state, leading to a second near-infrared (NIR-II, 1000–1700 nm) phosphorescent emission red-shift from 1088 to 1150 nm. This work not only provides vital insights into the relationship between structures and ground/excited states chiroptical activities at the single-atom level, but also presents bialkynyl as a promising stabilizing agent for building superatomic metal nanoclusters.

DOI: 10.1016/j.scib.2024.11.002

Source: https://www.sciencedirect.com/science/article/abs/pii/S2095927324007953