Synthesis of atomically precise Ag16 nanoclusters and investigating solvent-dependent ultrafast relaxation dynamics

Abstract

In this article, the main focus is to employ a new synthetic strategy to prepare atomically precise Ag nanoclusters (NCs) and unveil the critical role played by the solvents in the excited state dynamics of Ag NCs. The compositional analysis confirms the formula of the nanoclusters as Ag₁₆(PDT)₈(PPh₃)₄ (Ag-PDT NCs). These NCs showed a sharp absorption band at 525 nm and a comparatively broad absorption band at 633 nm. The emission maximum was 630 nm with a quantum yield (QY) of 0.23%. Three-component relaxation dynamics was retrieved from global analysis and described as core relaxation (664 fs), core-to-surface state relaxation (500 ps), and ground state relaxation (>1 ns) for Ag NCs in the DCM solvent. The time constants are slightly higher at 1.25 ps, 624.25 ps, and >1 ns for Ag NCs in the DMF solvent because of the less effective charge separation. The high QY in DMF follows this low charge separation (0.23% vs. 0.63%). The straight-chain dithiol capping agent (with lower electron density than an electron-rich aromatic ring) is mainly responsible for this less effective charge separation. Finding the pivotal role of the solvent in NC chemistry will help to characterize it thoroughly and produce a strategy for precise applications in various fields.