Anion‐Directed Regulation of Structures and Luminescence of Heterometallic Clusters

Abstract Anions have been used to regulate the structures and luminescence of heterometallic clusters. Introducing ClO 4 − into orange‐emissive, butterfly‐like [(C)(Au‐PPhpy 2 ) 6 Ag 4 ](BF 4 ) 6 ( 1 , PPhpy 2 =bis(2‐pyridyl)phenylphosphine) leads to the formation of red‐emissive [(C)(Au‐PPhpy 2 ) 6 Ag 5 (ClO 4 ) 3 ](ClO 4 ) 4 ( 2 ) with a novel trigonal bipyramidal structure; employing PhCO 2 − gives yellow‐emissive, hexagram‐like [(C)(Au‐PPhpy 2 ) 6 Ag 6 (PhCO 2 ) 3 ](BF 4 ) 5 ( 3 ). Notably, 1 exhibits weak luminescence in CH 2 Cl 2 /CH 3 OH=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.