Electron Transfer between [Au25(SC2H4Ph)18]-TOA+ and Oxoammonium Cations
Electron Transfer between [Au25(SC2H4Ph)18]-TOA+ and Oxoammonium Cations
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DOI：
10.1021/jz200925h
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发表时间：
2011-09-01
影响因子：
5.7
通讯作者：
Jin, Rongchao
中科院分区：
文献类型：
--
作者：
Liu, Zhao;Zhu, Manzhou;Jin, Rongchao
我们报道了2，2，6，6-四甲基哌啶-1-氧代四氟硼酸铵（克里思+BF 4-）与硫醇稳定的[Au-25（SC2 H4 Ph）（18）]（-）TOA（+）（简称Au-25（-））纳米团簇之间的分子间电子转移。克里思+阳离子通过哌啶氨基氧基自由基克里思（2，2，6，6-四甲基哌啶基-氧基）的单电子氧化产生。循环伏安法（CV）和电子自旋共振（ESR）明确表明克里思+阳离子与Au-25（-）纳米团簇之间发生了两个连续的单电子转移反应。核磁共振（H-1 NMR）分析表明，硫醇配体的亚甲基质子共振也可以用来监测氧化还原过程。紫外-可见光谱分析揭示了Au-25纳米团簇与克里思+阳离子之间连续单电子转移后吸收峰的变化。对涉及克里思+的氧化还原过程的容易控制允许制备纯Au-25（SC2 H4 Ph）（18）（+）纳米团簇。Au-25（SR）（18）团簇有趣的给电子性质可能在未来的研究中找到一些有前途的应用。
We report intermolecular electron transfer between 2,2,6,6-tetramethylpiperidin-1-oxoammonium tetrafluoroborate (TEMPO+BF4-) and thiol-stabilized [Au-25(SC2H4Ph)(18)](-)TOA(+) (abbreviated as Au-25(-)) nanoclusters. The TEMPO+ cations are generated by single electron oxidation of piperidine aminoxyl radical TEMPO (2,2,6,6-tetramethylpiperidinyl-oxy). Cyclic voltammetry (CV) and electron spin resonance (ESR) explicitly indicate that two consecutive single-electron transfer reactions occur between TEMPO+ cations and Au-25(-) nanoclusters. Nuclear magnetic resonance (H-1 NMR) analysis demonstrates that the methylene proton resonances of the thiolate ligands can also be used to monitor the redox process. UV-vis spectroscopic analysis reveals the changes in the absorption peaks of Au-25 nanoclusters upon consecutive single-electron transfers between the nanoclusters and TEMPO+ cations. The ease of control over the redox process involving TEMPO+ allows the preparation of pure Au-25(SC2H4Ph)(18)(+) nanoclusters. The interesting electron-donating properties of Au-25(SR)(18) clusters may find some promising applications in future studies.