Controlling the Phosphine Ligands of Pt₁Ag₂₈(S-Adm)₁₈(PR₃)₄ Nanoclusters

The precise manipulation of nanocluster structures remains highly desirable for disclosing the structure-property correlations at the atomic level. However, the control over a nanocluster (metal kernel + surface ligand) with a maintained template has long been a challenging pursuit, and little has been achieved for manipulation at the atomic level. Here, on the basis of the M₂₉(SR)₁₈(PR'₃)₄ cluster system, the control over the vertex phosphine ligands is accomplished. Therefore, a combination of the manipulation of vertex phosphines in this work and of internal metals and surface thiols reported previously realizes control over the M₂₉(SR)₁₈(PR'₃)₄ cluster template. The principles for regulating the photoluminescence (PL) of M₂₉ clusters via dictation of their metal compositions, surface thiols, and vertex phosphines are exploited to rationally design the most emissive nanocluster among the M₂₉ cluster family. Overall, this work fills the missing part necessary for the manipulation of M₂₉(SR)₁₈(PR'₃)₄ nanoclusters, providing an ideal nanomodel that enables us to grasp the structure-property correlations at the atomic level.