Tailoring the Electron–Phonon Interaction in Au₂₅(SR)₁₈ Nanoclusters via Ligand Engineering and Insight into Luminescence

Understanding the electron-phonon interaction in Au nanoclusters (NCs) is essential for enhancing and tuning their photoluminescence (PL) properties. Among all the methods, ligand engineering is the most straightforward and facile one to design Au NCs with the desired PL properties. However, a systematic understanding of the ligand effects toward electron-phonon interactions in Au NCs is still missing. Herein, we synthesized four Au25(SR)18- NCs protected by different -SR ligands and carefully examined their temperature-dependent band-gap renormalization behavior. Data analysis by a Bose-Einstein two-oscillator model revealed a suppression of high-frequency optical phonons in aromatic-ligand-protected Au25 NCs. Meanwhile, a low-frequency breathing mode and a quadrupolar mode are attributed as the main contributors to the phonon-assisted nonradiative relaxation pathway in aromatic-ligand-protected Au25 NCs, which is in contrast with non-aromatic-ligand-protected Au25 NCs, in which tangential and radial modes play the key roles. The PL measurements of the four Au25 NCs showed that the suppression of optical phonons led to higher quantum yields in aromatic-ligand-protected Au25 NCs. Cryogenic PL measurements provide insights into the nonradiative energy relaxation, which should be further investigated for a full understanding of the PL mechanism in Au25 NCs.