Polyhedral {Ag12} and {Ag16} Clusters: Synthesis, Structural Characterization and Third‐Order Nonlinear Optical Properties

Abstract Two polyhedral silver‐thiolate clusters, [S@Ag 16 (Tab) 10 (MeCN) 8 ](PF 6 ) 14 ( Ag 16 ) and [Ag 12 (Tab) 6 (DMF) 12 ](PF 6 ) 12 ( Ag 12 ), were synthesized by using electroneutral Tab species as protective ligands (Tab=4‐(trimethylammonio)benzenethiolate, DMF= N,N ‐dimethylformamide, MeCN=acetonitrile). Ag 16 has a decahedral shape composed of eight pentagon {Ag 5 } units and two square {Ag 4 } units. The structure of Ag 12 is a cuboctahedron, a classical Archimedean structure composed of six triangular faces and eight square faces. The former configuration is discovered in silver‐thiolate cluster for the first time, possibly benefited from the more flexible coordination between the Tab ligand and Ag + facilitated by the electropositive −N(CH 3 ) 3 + substituent group. Third‐order nonlinear optical studies show that both clusters in DMF exhibit reverse saturate absorption response under the irradiation of 532 nm laser.