Tetrahedral Geometry Induction of Stable Ag–Ti Nanoclusters by Flexible Trifurcate TiL₃ Metalloligand

A series of increasingly large silver nanoclusters with a varied combination of Archimedean and/or Platonic solid arrangements was constructed using a flexible trifurcate TiL₃ (L = Salicylic acid or 5-fluorosalicylic acid) metalloligand: Ag₄@Ag₄@Ti₄ (PTC-85), Ag₁₂@Ti₄ (PTC-86), Ag₄@Ag₆@Ag₁₂@Ti₄ (PTC-87), Ag₆@Ag₂₄@Ag₁₂@Ti₄ (PTC-88), and Ag₁₂@Ag₂₄@Ti₄ (PTC-89). The silver nanoclusters are each capped by four TiL₃ moieties, thereby forming {Ti₄} supertetrahedra with average edge lengths ranging from ∼8.12 Å to ∼17.37 Å. Such {Ti₄} moieties further induce the tetrahedral geometry of the encapsulated silver nanoclusters. These atomically precise metallic clusters were found to be ultrastable with respect to air for several months, and to water for more than 3 days, due to the stabilizing effects of the TiL₃ metalloligand. Moreover, the obtained clusters exhibit nonlinear optical (NLO) effects in optical limiting tests and also temperature-dependent photoluminescent properties. This work provides an interesting metalloligand method not only to induce the spatial growth of metallic clusters to achieve highly symmetric structures, but also to enhance their stability which is crucial for future application.