Rapid screening and separation of fluorescent clusters: a case study of Au9Cu5
Jianwei Li1, Jing Wang1, Qinzhen Li1
1Institutes of Physical Science and Information Technology, Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Key Laboratory of Structure and Functional Regulation of Hybrid Materials of Ministry of Education, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei, Anhui 230601, China. gaoguiqi1@126.com.
Abstract:
The rapid pre-screening and separation of strongly fluorescent clusters are critical for advancing research on fluorescent cluster properties and applications. However, these methods remain unexplored for oil-soluble clusters. In this work, the strong fluorescence characteristics of clusters enable rapid screening and separation of Au9Cu5 from mixed clusters via thin-layer chromatography (TLC). The Au9Cu5 cluster features an icosahedral Au9Cu4 core, shielded by a (DPPP)2CuCl2 motif, four DPPP ligands, and two Cl atoms, with the overall charge stabilized by two BPh4- counterions. Using chair BDPP instead of DPPP, optically active R/S-Au9Cu5 clusters were synthesized, exhibiting a dissymmetry factor (g) of 0.75 × 10-4-a moderate value among clusters. This arises primarily because the introduction of R/S-BDPP distorts only the cluster's surface motif, while the core retains high symmetry, with chiral signals still predominantly originating from ligand-to-metal charge transfer (LMCT). Further comparison of fluorescence properties reveals a 3-fold enhancement in the quantum yield of R/S-Au9Cu5 over Au9Cu5 (6.5% vs. 2.0%). Structural analysis attributes this improvement to the closer proximity of peripheral metal atoms to the core in R/S-Au9Cu5.
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