Abstract
AbstractAnions 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,1exhibits 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 for2and3, respectively. Theoretical calculation confirms that the involvement of anions in the electronic structures is responsible for the shifts of emission. The high QYs of2and3are 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.
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