Anion‐Directed Regulation of Structures and Luminescence of Heterometallic Clusters. Issue 25 (25th April 2022)

• Record Type: Journal Article
• Authors: Li, Jiao‐Jiao; Liu, Chun‐Yu; Guan, Zong‐Jie; Lei, Zhen; Wang, Quan‐Ming
• Is Part Of: Angewandte Chemie international edition. Volume 61:Issue 25(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-04-25
• Subjects: Anions -- Cluster Compounds -- Gold -- Luminescence -- Silver; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202201549
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Anions have been used to regulate the structures and luminescence of heterometallic clusters. Introducing ClO4 − into orange‐emissive, butterfly‐like [(C)(Au‐PPhpy2 )6 Ag4 ](BF4 )6 (1, PPhpy2 =bis(2‐pyridyl)phenylphosphine) leads to the formation of red‐emissive [(C)(Au‐PPhpy2 )6 Ag5 (ClO4 )3 ](ClO4 )4 (2 ) with a novel trigonal bipyramidal structure; employing PhCO2 − gives yellow‐emissive, hexagram‐like [(C)(Au‐PPhpy2 )6 Ag6 (PhCO2 )3 ](BF4 )5 (3 ). Notably, 1 exhibits weak luminescence in CH2 Cl2 /CH3 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. Abstract : Anions were employed to direct the regulation of the structures and luminescence of heterometallic clusters. Two novel clusters with triangular bipyramidal CAu6 Ag5 (2 ) and hexagram‐like CAu6 Ag6 (3 ) cores were obtained from the CAu6 Ag4 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 .