科研之友
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摘要
Anions have been used to regulate the structures and luminescence of heterometallic clusters. Introducing ClO4? into orange‐emissive, butterfly‐like [(C)(Au‐PPhpy2)6Ag4](BF4)6 (1, PPhpy2=bis(2‐pyridyl)phenylphosphine) leads to the formation of red‐emissive [(C)(Au‐PPhpy2)6Ag5(ClO4)3](ClO4)4 (2) with a novel trigonal bipyramidal structure; employing PhCO2? gives yellow‐emissive, hexagram‐like [(C)(Au‐PPhpy2)6Ag6(PhCO2)3](BF4)5 (3). Notably, 1 exhibits weak luminescence in CH2Cl2/CH3OH=1?:?1 (v?:?v) with a quantum yield (QY) of 0.05, whereas it was dramatically increased to 0.49 and 0.83 for 2 and 3, respectively. Theoretical calculation confirms that the involvement of anions in the electronic structures is responsible for the shifts of emission. The high QYs of 2 and 3 are attributed to the protection provided by ligands and anions. This work demonstrates that anions may serve as an extra designable factor beyond just counterions for functional metal clusters.(#br)Anions were employed to direct the regulation of the structures and luminescence of heterometallic clusters. Two novel clusters with triangular bipyramidal CAu6Ag5 (2) and hexagram‐like CAu6Ag6 (3) cores were obtained from the CAu6Ag4 type precursor 1. They exhibit red‐ or blue‐shifted luminescence, respectively. Remarkably, the quantum yields of 2 and 3 are one order of magnitude higher than 1.
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