Cl@Ag₂₂ Au₆ (4-TBBT)₂₈ (PPh₄ ): A Chloride-Centered Ag-Au Bimetallic Cluster for Optics

We report the single-crystal synthesis of a chlorine-centered bimetallic cluster, Cl@Ag₂₂ Au₆ (4-TBBT)₂₈ (PPh₄ ), which bears a quatrefoil-structured Cl@Ag₂₂ (SR)₁₆ core studded by six Au(SR)₂ staples showing a quasi T_d symmetry. This cluster bears 28 metal atoms and 28 ligands, with a chlorine atom hosted in the center of the metallic Ag₂₂ Au₆ core. Single-crystal analysis shows that this cluster possesses essentially a different bonding nature compared with other monolayer-protected metal clusters (MPCs) or traditional metal-sulfur complexes. We fully dissect the structure evolution in forming such a chlorine-centered cluster. Interestingly, this cluster, Cl@Ag₂₂ Au₆ (4-TBBT)₂₈ (PPh₄ ), displays a fluorescence emission at 570 nm and supports the solid emission with a minor red shift at 574 nm. On the other hand, we have tested the nonlinear optical property and observed unambiguous nonlinear optical property with a normal valley-shaped transmittance curve corresponding to reverse saturated absorption (RSA) of the cluster.