Cooperative Construction of Silver(I) Nanoclusters of Primary–Tertiary Diphosphine Directed by Thiolate Templates Through Ligand Metathesis

Abstract

In this work, a diphosphine chelator, 2-Ph₂PC₆H₄PH₂, containing both primary and tertiary phosphine donors, was used to create highly stable silver(I) nanoclusters through a dynamic ligand metathesis reaction. Taking advantage of thiolate-silver coordination polymers as synthetic precursors, we developed a viable synthetic approach to access Ag34 nanoclusters through dual proton and ligand exchange successfully. Owing to the stronger coordination ability of the bifunctional 2-Ph₂PC₆H₄PH₂ ligand, substitution results in the formation of thermodynamically stable Ag34 nanoclusters linked by fifteen 2-Ph₂PC₆H₄P²⁻ chelators. Notably, thiolates as structural templates rather than protective ligands play a crucial role in directing nanocluster construction. The Ag34 nanoclusters manifest highly efficient near-infrared photoluminescence peaked at ca. 800 nm with over 24% of quantum yield in fluid CH₂Cl₂ solution, arising mostly from ligand-to-metal charge transfer (³LMCT) and cluster-centered (³CC) triplet states. Solution-processable near-infrared organic light-emitting diodes (NIR-OLEDs) achieved high-efficiency near-infrared electroluminescence with an external quantum efficiency (EQE) of 10.2%. The unique synthetic approach can be extended to other metal systems, thereby expanding both the structural diversity and application potential of metal nanoclusters.

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