Impact of Ligands on Structural and Optical Properties of Ag₂₉ Nanoclusters

A ligand exchange strategy has been employed to understand the role of ligands on the structural and optical properties of atomically precise 29 atom silver nanoclusters (NCs). By ligand optimization, ∼44-fold quantum yield (QY) enhancement of Ag₂₉(BDT)_12-(DHLA) NCs (x = 1-6) was achieved, where BDT and DHLA refer to 1,3-benzene-dithiol and dihydrolipoic acid, respectively. High-resolution mass spectrometry was used to monitor ligand exchange, and structures of the different NCs were obtained through density functional theory (DFT). The DFT results from Ag₂₉(BDT)₁₁(DHLA) NCs were further experimentally verified through collisional cross-section (CCS) analysis using ion mobility mass spectrometry (IM MS). An excellent match in predicted CCS values and optical properties with the respective experimental data led to a likely structure of Ag₂₉(DHLA)₁₂ NCs consisting of an icosahedral core with an Ag₁₆S₂₄ shell. Combining the experimental observation with DFT structural analysis of a series of atomically precise NCs, Ag_29-Au(BDT)_12-(DHLA) (where y, x = 0,0; 0,1; 0,12 and 1,12; respectively), it was found that while the metal core is responsible for the origin of photoluminescence (PL), ligands play vital roles in determining their resultant PLQY.