Assembly-induced spin transfer and distance-dependent spin coupling in atomically precise AgCu nanoclusters

• Published in: Nature communications 2022-10, Vol.13 (1), p.5934-11, Article 5934
• Main Authors: Xia, Nan, Xing, Jianpei, Peng, Di, Ji, Shiyu, Zha, Jun, Yan, Nan, Su, Yan, Jiang, Xue, Zeng, Zhi, Zhao, Jijun, Wu, Zhikun
• Format: Article
• Language: English
• Subjects: 119/118; 140/146; 140/58; 147/143; 639/301/357/354; 639/638/298/920; 639/925/357/537; Clusters; Coupling; Crystallography; Functional materials; Humanities and Social Sciences; Isotropy; Magnetic moments; Mass spectrometry; Mass spectroscopy; multidisciplinary; Nanoclusters; Nanoparticles; Paramagnetism; Science; Science (multidisciplinary); Single crystals; Sulfur; Superstructures; X-ray crystallography
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-33651-9

Nanoparticle assembly paves the way for unanticipated properties and applications from the nanoscale to the macroscopic world. However, the study of such material systems is greatly inhibited due to the obscure compositions and structures of nanoparticles (especially the surface structures). The assembly of atomically precise nanoparticles is challenging, and such an assembly of nanoparticles with metal core sizes strictly larger than 1 nm has not been achieved yet. Here, we introduced an on-site synthesis-and-assembly strategy, and successfully obtained a straight-chain assembly structure consisting of Ag 77 Cu 22 (CHT) 48 (CHT: cyclohexanethiolate) nanoparticles with two nanoparticles separated by one S atom, as revealed by mass spectrometry and single crystal X-ray crystallography. Although Ag 77 Cu 22 (CHT) 48 bears one unpaired shell-closing electron, the magnetic moment is found to be mainly localized at the S linker with magnetic isotropy, and the sulfur radicals were experimentally verified and found to be unstable after disassembly, demonstrating assembly-induced spin transfer. Besides, spin nanoparticles are found to couple and lose their paramagnetism at sufficiently short inter-nanoparticle distance, namely, the spin coupling depends on the inter-nanoparticle distance. However, it is not found that the spin coupling leads to the nanoparticle growth. The assembly of atomically precise clusters into ordered superstructures enables new functional material designs. Here, the authors propose a strategy for linear arrangements of AgCu clusters and explore the consequent transfer and coupling of magnetic spins.