Abstract
As versatile ligands with extraordinary coordination capabilities, RPH(2) (R = alkyl or aryl) are rarely used in constructing metal nanoclusters due to their volatility, toxicity, spontaneous flammability, and susceptibility to oxidation. In this work, we designed a primary and tertiary phosphorus-bound diphosphine chelator (2-Ph(2)PC(6)H(4)PH(2)) to create ultrastable silver nanoclusters with metallic aromaticity. By controlling the deprotonation rate of 2-Ph(2)PC(6)H(4)PH(2) and adjusting the templates, we successfully synthesized two near-infrared emissive nanoclusters, Ag30 and Ag32, which have analogous icosidodecahedral Ag(30) shells with an I(h) symmetry. Deprotonated ligand (2-Ph(2)P(α)C(6)H(4)P(β)(2-)) exhibits a coordination mode of μ(5)-η(1)(P(β)),η(2)(P(α),P(β)), which endows a unique metallic aromaticity to Ag30 and Ag32. The solution-processed organic light-emitting diodes based on Ag30 achieve an external quantum efficiency of 15.1%, representing the breakthrough in application of silver nanoclusters to near-infrared-emitting devices. This work represents a special ligand system for synthesizing ligand-protected coinage metal nanoclusters and opens up horizons of creating nanoclusters with distinct geometries and metal aromaticity.