激发态
电子转移
纳米团簇
化学
质子耦合电子转移
质子
光致发光
电子
猝灭(荧光)
金属
原子物理学
化学物理
光化学
材料科学
荧光
物理
量子力学
光电子学
有机化学
作者
Kai-Yuan Huang,Yanyan Chen,Wen‐Lu Wang,Wei‐Ming Sun,Zhen Lin,Qiaofeng Yao,Wei Chen,Jianping Xie,Hao‐Hua Deng
标识
DOI:10.1002/anie.202418560
摘要
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 pKa of the ligands, the emission performance of Au25(SR)18 can be easily regulated in physiological environments.
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