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‐Ph 2 PC 6 H 4 PH 2 , 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‐Ph 2 PC 6 H 4 PH 2 ligand, substitution results in the formation of thermodynamically stable Ag34 nanoclusters linked by fifteen 2‐Ph 2 PC 6 H 4 P 2− 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 CH 2 Cl 2 solution, arising mostly from ligand‐to‐metal charge transfer ( 3 LMCT) and cluster‐centered ( 3 CC) 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.