Synergistic coordination of diphosphine with primary and tertiary phosphorus centers: Ultrastable icosidodecahedral Ag<sub>30</sub> nanoclusters with metallic aromaticity.
basic_science · Level V
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- Record sourced from PubMed, PMID 39602534.
- Also identified by DOI 10.1126/sciadv.ads0728 and PMC identifier 11601195.
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Abstract
As versatile ligands with extraordinary coordination capabilities, RPH<sub>2</sub> (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<sub>2</sub>PC<sub>6</sub>H<sub>4</sub>PH<sub>2</sub>) to create ultrastable silver nanoclusters with metallic aromaticity. By controlling the deprotonation rate of 2-Ph<sub>2</sub>PC<sub>6</sub>H<sub>4</sub>PH<sub>2</sub> and adjusting the templates, we successfully synthesized two near-infrared emissive nanoclusters, <b>Ag30</b> and <b>Ag32</b>, which have analogous icosidodecahedral Ag<sub>30</sub> shells with an <i>I</i><sub>h</sub> symmetry. Deprotonated ligand (2-Ph<sub>2</sub>P<sub>α</sub>C<sub>6</sub>H<sub>4</sub>P<sub>β</sub><sup>2-</sup>) exhibits a coordination mode of μ<sub>5</sub>-η<sup>1</sup>(P<sub>β</sub>),η<sup>2</sup>(P<sub>α</sub>,P<sub>β</sub>), which endows a unique metallic aromaticity to <b>Ag30</b> and <b>Ag32</b>. The solution-processed organic light-emitting diodes based on <b>Ag30</b> 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.