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Alkynyl-Protected Ag12Cu4 Cluster with Aggregation-Induced Emission Enhancement

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Title
Alkynyl-Protected Ag12Cu4 Cluster with Aggregation-Induced Emission Enhancement
Author(s)
Guocheng Deng; Kangjae Lee; Deng, Hongwen; Megalamane S. Bootharaju; Zheng, Nanfeng; Taeghwan Hyeon
Publication Date
2022-12
Journal
JOURNAL OF PHYSICAL CHEMISTRY C, v.126, no.48, pp.20577 - 20583
Publisher
AMER CHEMICAL SOC
Abstract
Photoluminescence (PL) of atomically precise metal clusters is attractive for various applications, including light emission, chemical sensing, and bioimaging. Herein, we report the synthesis and total structure of an alkynyl-protected bimetallic AgCu cluster, Ag12Cu4(C-CR)14(PPh3)4 (Ag12Cu4: HC-CR = 3,5-bis(trifluoromethyl)phenylacetylene; PPh3 = triphenylphosphine), which exhibits crystallization-induced emission enhancement and aggregation-induced emission enhancement phenomena. As revealed by the single crystal X-ray diffraction data, the Ag12Cu4 cluster comprises an octahedron Ag6 core, which is stabilized by two large Ag3Cu2(C-CR)7(PPh3)2 metal-ligand motifs. The free valence electron count suggests that Ag12Cu4 is a two-electron superatom. Interestingly, the weak PL of Ag12Cu4 solution at approximate to 730 nm (near-infrared region) is found to be significantly enhanced in the solid state (15 and 8 fold respectively, for the crystalline and aggregated forms). A detailed structural analysis of the Ag12Cu4 cluster reveals the presence of abundant intercluster C-H center dot center dot center dot F interactions, which significantly restrict the intramolecular rotations and vibrations, leading to strong PL enhancement in the solid state. This work will trigger the studies of other alloy metal nanoclusters with promising photophysical properties for optoelectronic and other applications.
URI
https://pr.ibs.re.kr/handle/8788114/12521
DOI
10.1021/acs.jpcc.2c04782
ISSN
1932-7447
Appears in Collections:
Center for Nanoparticle Research(나노입자 연구단) > 1. Journal Papers (저널논문)
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