A Discrete Ligand-Free T3 Supertetrahedral Cluster of Gallium Sulfide

Abstract

Large discrete supertetrahedral clusters of metal chalcogenides are rare due to the difficulty of crystallizing solids in which the negative charge of the cluster is balanced by the positive charges of the countercations. Here, we describe a discrete ligand-free T3 supertetrahedral cluster, [Ga10S16(SH)4]6−, which was successfully synthesized in the presence of the superbase 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) using the neutral surfactant polyethyleneglycol (PEG)-400 as the reaction solvent. Protonated DBUH+ cations are incorporated into the crystal structure of the product, which can be formulated as [C9H17N2]6[Ga10S16(SH)4]. This compound, which represents the first example of a discrete ligand-free T3 cluster of gallium sulfide, was fully characterized by single-crystal and powder X-ray diffraction, elemental analysis, infrared spectroscopy, thermogravimetric analysis, and ultraviolet-visible diffuse reflectance. The results presented here indicate that the use of surfactants as solvents offers potential for the preparation of new compounds containing supertetrahedral clusters.

Keywords

• supertetrahedral cluster
• gallium sulfide
• crystal structure