Ag44(EBT)26(TPP)4 Nanoclusters With Tailored Molecular and Electronic Structure

Abstract Although atomically precise metalloid nanoclusters (NCs) of identical size with distinctly different molecular structures are highly desirable to understand the structural effects on the optical and photophysical properties, their synthesis remains highly challenging. Herein, we employed phosphine and thiol capping ligands featuring appropriate steric effects and synthesized a charge‐neutral Ag NC with the formula Ag 44 (EBT) 26 (TPP) 4 (EBT: 2‐ethylbenzenethiolate; TPP: triphenylphosphine). The single‐crystal X‐ray structure reveals that this NC has a hollow metal core of Ag 12 @Ag 20 and a metal–ligand shell of Ag 12 (EBT) 26 (TPP) 4 . The presence of mixed ligands and long V‐shaped metal–ligand motifs on this NC has resulted in an enhancement of the NIR‐II photoluminescence quantum yield by >25‐fold compared to an all‐thiolate‐stabilized anionic [Ag 44 (SR) 30 ] 4− NC (SR: thiolate). Time‐dependent density‐functional calculations show that our Ag 44 NC is an 18‐electron superatom with a modulated electronic structure as compared to the [Ag 44 (SR) 30 ] 4− anion, significantly influencing its optical properties.