Affiliation:
1. College of Chemistry Chemical Engineering and Materials Science Soochow University Suzhou Jiangsu 215123 China
2. State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry Chinese Academy of Sciences Shanghai 200023 China
3. College of Physical Science and Technology Soochow University Suzhou 215006 Jiangsu China
Abstract
AbstractTwo polyhedral silver‐thiolate clusters, [S@Ag16(Tab)10(MeCN)8](PF6)14 (Ag16) and [Ag12(Tab)6(DMF)12](PF6)12 (Ag12), were synthesized by using electroneutral Tab species as protective ligands (Tab=4‐(trimethylammonio)benzenethiolate, DMF=N,N‐dimethylformamide, MeCN=acetonitrile). Ag16 has a decahedral shape composed of eight pentagon {Ag5} units and two square {Ag4} units. The structure of Ag12 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(CH3)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.
Funder
National Natural Science Foundation of China
Collaborative Innovation Center of Suzhou Nano Science and Technology
Priority Academic Program Development of Jiangsu Higher Education Institutions
Natural Science Foundation of Jiangsu Province
China Postdoctoral Science Foundation