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

Although atomically precise metalloid nanoclusters (NCs) of identical size with distinctly different molecular structures are highly desirable to understand the structural effects on optical and photophysical properties, their synthesis remains challenging. Herein, we employed phosphine thiol capping ligands featuring appropriate steric synthesized a charge-neutral Ag NC formula Ag44 (EBT)26 (TPP)4 (EBT: 2-ethylbenzenethiolate; TPP: triphenylphosphine). The single-crystal X-ray structure reveals that this has hollow metal core Ag12 @Ag20 metal-ligand shell . presence mixed long V-shaped motifs resulted in an enhancement NIR-II photoluminescence quantum yield by >25-fold compared all-thiolate-stabilized anionic [Ag44 (SR)30 ]4- (SR: thiolate). Time-dependent density-functional calculations show our is 18-electron superatom modulated electronic as anion, significantly influencing its properties.