Silver-Sulfur Hybrid Supertetrahedral Clusters: The Hitherto Missing Members in the Metal-Chalcogenide Tetrahedral Clusters

The synthesis of Group 11 metal chalcogenide supertetrahedral clusters (SCs) still remains a great challenge mainly due to the high tendency of metal aggregation through metallophilicity and global charge balance. Demonstrated herein are the preparation, crystallographic characterization, and optical properties of two stable silver-sulfur SCs through ligand-control; one as a discrete zero-dimensional (0D) V3,4-type cluster and the other as a one-dimensional (1D) zigzag chain extended by alternating V3,2-type clusters. The notation Vn,m (where n is the number of metal layers, and m is the number of vacant corners) is used to describe a new series of vacant-corner SCs, which can be derived from the regular Tn clusters. The existence of vacant-corner-type SCs may be ascribed to the low valence and tri-coordinated environment of silver ions. These are the first representatives of str(u)cturally determined silver-sulfur tetrahedral clusters thus far. This work enriches the coinage-metal chalcogenide tetrahedral cluster portfolio, discovers vacant-corner SCs present in silver-sulfur hybrid tetrahedral clusters, and provides effective means for further development of Group 11 coinage-metal chalcogenide SCs.