Single-atom "surgery" on chiral all-dialkynyl-protected superatomic silver nanoclusters

Chengkai Zhang; Wei-Dan Si; Wei-Dong Tian; Wan-Jun Xiao; Zhi-Yong Gao; Zhi Wang; Chen-Ho Tung; Di Sun

doi:10.1016/j.scib.2024.11.002

Single-atom "surgery" on chiral all-dialkynyl-protected superatomic silver nanoclusters

Sci Bull (Beijing). 2024 Nov 4:S2095-9273(24)00795-3. doi: 10.1016/j.scib.2024.11.002. Online ahead of print.

Authors

Chengkai Zhang¹, Wei-Dan Si¹, Wei-Dong Tian¹, Wan-Jun Xiao¹, Zhi-Yong Gao², Zhi Wang¹, Chen-Ho Tung¹, Di Sun³

Affiliations

¹ School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China.
² School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China.
³ School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, China. Electronic address: dsun@sdu.edu.cn.

PMID: 39562187
DOI: 10.1016/j.scib.2024.11.002

Abstract

The manipulation of single atom 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 Ag^40th 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.

Keywords: Chiral bialkynyl ligands; NIR-II phosphorescence; Single atom manipulation; Superatomic silver nanoclusters.