摘要/Abstract

通过可控的方式精确调控纳米粒子的结构仍是一个富有挑战性和鼓舞人心的课题.尽管单原子或两、三个金属原子的精细调控已经在金纳米粒子中实现，涉及三个以上金属原子的取代（模块取代）还没有报道.本工作报道了环己硫醇配体保护的Au₄₈（CHT）₂₆的合成及其通过赝反伽伐尼过程的模块取代.单晶结构揭示模块取代的产物与母体团簇共用一个相似的Au₃₁（CHT）₁₂主体，但剩余部分不同（Au₆（CHT）₁₁ vs.Au₁₆（CHT）₁₄）.一个有趣的发现是模块取代抑制了Au₄₈（CHT）₂₆的光热过程，却增强了它的发射，赋予了所合成团簇更好的双（多）功能应用潜力.光热效应的减弱和发射的增强也暗示了这两种作用能够彼此至少部分转化，对于研究这两种效应之间的相互影响也具有重要的启示.
关键词: 金纳米团簇, 模块替换, 赝反伽伐尼反应, 光热效应, 荧光
Precisely modulating the structure of nanoparticles in a controlled manner is still a challenging and inspiring topic. Although the single or few-metal atom tailoring of gold nanoparticles has been reported, local structural replacement involving over three net metal atoms (module replacement, MR) has not been hitherto achieved. Herein, we report the synthesis of cyclohexanethiolated metal nanoclusters (NCs) Au₄₈(CHT)₂₆ and their MR by a so-called pseudo-anti-galvanic reaction (AGR) process. The MR product Au₃₇(CHT)₂₃ shares a similar Au₃₁(CHT)₁₂ unit with its predecessor Au₄₈(CHT)₂₆; however, it differs from its predecessor in the remaining section (Au₆(CHT)₁₁ vs. Au₁₆(CHT)₁₄), as revealed by single-crystal X-ray crystallography (SCXC). Interestingly, the MR inhibits the photothermy but enhances the emission of Au₄₈(CHT)₂₆ NCs, which might endow the as-obtained NC better potential for bi(multiple)-functional application. The counter effects of the MR on the emission and photothermy indicate that photoluminescence and photothermy can be at least partly converted into each other, which has some important implications for the understanding of their interaction.
Key words: gold nanoparticles, module replacement, pseudo-anti-galvanic reaction (AGR), photothermy, photoluminescence


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