Nanocluster growth via “graft-onto”: effects on geometric structures and optical properties

Abstract

Atomically precise engineering on the nanocluster surface remains highly desirable for the fundamental understanding of how surface structures of a nanocluster contribute to its overall properties. In this paper, the concept of “graft-onto” has been exploited to facilitate nanocluster growth on surface structures. Specifically, the Ag₂(DPPM)Cl₂ complex is used for re-constructing the surface structure of Pt₁Ag₂₈(SR)₁₈(PPh₃)₄ (Pt₁Ag₂₈, SR = 1-adamantanethiolate) and producing a size-growth nanocluster – Pt₁Ag₃₁(SR)₁₆(DPPM)₃Cl₃ (Pt₁Ag₃₁). The grafting effect of Ag₂(DPPM)Cl₂ induces both direct changes on the surface structure (e.g., size growth, structural transformation, and surface rotation) and indirect changes on the kernel structure (from a fcc configuration to an icosahedral configuration). Remarkable differences have been observed by comparing optical properties between Pt₁Ag₂₈ and Pt₁Ag₃₁. Significantly, Pt₁Ag₃₁ exhibits high photo-luminescent intensity with a quantum yield of 29.3%, which is six times that of the Pt₁Ag₂₈. Overall, this work presents a new approach (i.e., graft-onto) for the precise dictation of nanocluster surface structures at the atomic level.