Bulky Surface Ligands Promote Surface Reactivities of [Ag 141 X 12 (S-Adm) 40 ] 3+ (X = Cl, Br, I) Nanoclusters: Models for Multiple-Twinned Nanoparticles.

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 [Ag ₁₄₁ X ₁₂ (S-Adm) ₄₀ ] ³⁺ (where X = Cl, Br, I; S-Adm = 1-adamantanethiolate) has a multiple-shell structure with an Ag ₇₁ core protected by a shell of Ag ₇₀ X ₁₂ (S-Adm) ₄₀ . The Ag ₇₁ core can be considered as 20 frequency-two Ag ₁₀ 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.