The Hidden Mechanism: Excited‐State Proton‐Electron Pair Transfer in Metal Nanocluster Emission

Comprehending the underlying factors that govern photoluminescence (PL) in metal nanoclusters (NCs) under physiological conditions remains a highly intriguing and unresolved challenge, particularly for their biomedical applications. In this study, we evaluate the critical role of excited-state proton-coupled electron transfer in the emission of metal NCs. Our findings demonstrate that hydronium ion (H₃O⁺) binding can trigger a nonlinear, pH-dependent excited-state concerted electron proton transfer (CEPT) reaction. This involves simultaneous electron transfer from the Au(0) core to the Au(I)-ATT (ATT denotes 6-aza-2-thiothymidine) surface and proton transfer from H₃O⁺ to the ATT ligand in a single step, greatly promoting vibrations and rotations of the Au(I)-ATT surface, resulting in substantial PL quenching of Au₁₀(ATT)₆ NCs. Further analyses show that the unique CEPT dynamics are strongly influenced by the opposing effects of increased reorganization energy and a larger pre-exponential factor on the electron transfer rate. Moreover, the proposed excited-state CEPT process is found to be prevalent in core-shell relaxation metal NCs, such as Au₂₅(SR)₁₈ (SR denotes thiolate) NCs, and serves as an important factor in limiting their PL emission. By simply controlling the pK_a of the ligands, the emission performance of Au₂₅(SR)₁₈ can be easily regulated in physiological environments.