Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory for Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University , Xiamen 361005, China.
Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä , FI-40014 Jyväskylä, Finland.
J Am Chem Soc. 2017 Sep 27;139(38):13288-13291. doi: 10.1021/jacs.7b07926. Epub 2017 Sep 18.
Surface ligands play important roles in controlling the size and shape of metal nanoparticles and their surface properties. In this work, we demonstrate that the use of bulky thiolate ligands, along with halides, as the surface capping agent promotes the formation of plasmonic multiple-twinned Ag nanoparticles with high surface reactivities. The title nanocluster [AgX(S-Adm)] (where X = Cl, Br, I; S-Adm = 1-adamantanethiolate) has a multiple-shell structure with an Ag core protected by a shell of AgX(S-Adm). The Ag core can be considered as 20 frequency-two Ag tetrahedra fused together with a dislocation that resembles multiple-twinning in nanoparticles. The nanocluster has a strong plasmonic absorption band at 460 nm. Because of the bulkiness of S-Adm, the nanocluster has a low surface thiolate coverage and thus unusually high surface reactivities toward exchange reactions with different ligands, including halides, phenylacetylene and thiols. The cluster can be made water-soluble by metathesis with water-soluble thiols, thereby creating new functionalities for potential bioapplications.
表面配体在控制金属纳米粒子的尺寸和形状及其表面性质方面起着重要作用。在这项工作中，我们证明了使用庞大的硫醇配体以及卤化物作为表面封端剂，可以促进具有高表面反应性的等离子体多孪晶 Ag 纳米粒子的形成。标题纳米团簇[AgX(S-Adm)]（其中 X = Cl、Br、I；S-Adm = 1-金刚烷硫醇）具有多壳层结构，Ag 核被 AgX(S-Adm)壳保护。Ag 核可以被认为是由 20 个频率为二的 Ag 四面体融合在一起形成的，其中存在类似于纳米粒子中的孪晶位错。该纳米团簇在 460nm 处具有强等离子体吸收带。由于 S-Adm 的庞大性，纳米团簇的表面硫醇覆盖率较低，因此对与不同配体（包括卤化物、苯乙炔和硫醇）的交换反应具有异常高的表面反应性。通过与水溶性硫醇的复分解反应，该团簇可以变得水溶性，从而为潜在的生物应用创造新的功能。
