Anion‐Directed Regulation of Structures and Luminescence of Heterometallic Clusters
Jiaojiao Li, Chunyu Liu, Zong‐Jie Guan, Zhen Lei, Quan‐Ming Wang
Abstract
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.