3 years ago

Full Protection of Intensely Luminescent Gold(I)–Silver(I) Cluster by Phosphine Ligands and Inorganic Anions

Full Protection of Intensely Luminescent Gold(I)–Silver(I) Cluster by Phosphine Ligands and Inorganic Anions
Quan-Ming Wang, Xiao-Li Pei, Zhen Lei, Zong-Jie Guan
An intensely luminescent gold(I)–silver(I) cluster [(C)(AuPPhpy2)6Ag6(CF3CO2)3](BF4)5 (PPhpy2=bis(2-pyridyl)phenylphosphine) (3) is synthesized by the reaction of [(C)(AuPPhpy2)6Ag4](BF4)6 with AgCF3CO2. All eight faces of the octahedral C@Au6 core in 3 are capped, that is, six faces are capped by silver ions and two by tetrafluoroborates. Cluster 3 is intensely luminescent in solution with a quantum yield of 92 %. Ligation of CF3CO2− ions is vital for the construction and emission properties of 3, as confirmed by DFT calculations. BF4− ions are involved in the protecting sphere of the metal core, as evidenced by 19F NMR data. The participation of phosphines, CF3CO2−, and BF4− ions in the protection of the emissive core and the enhancement of the rigidity of the cluster result in the high emission efficiency. This is the first example of organic ligands and inorganic anions forming a rigid protecting sphere for luminescent coinage-metal clusters. Small anions play a big role in the formation of the intensely luminescent gold(I)–silver(I) cluster [(C)(AuPPhpy2)6Ag6(CF3CO2)3](BF4)5 (PPhpy2=bis(2-pyridyl)phenylphosphine). This is the first example employing organic ligands and inorganic anions in the construction of a rigid protecting sphere for luminescent coinage-metal clusters.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201702522

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