Mixed Solvothermal Synthesis of Tn Cluster-Based Indium and Gallium Sulfides Using Versatile Ammonia or Amine...

Metal chalcogenide supertetrahedral Tn clusters are of current interest for their unique compositions and structures, which rely highly on the structure-directing agents. Herein, we report four novel Tn cluster-based indium and gallium sulfides, namely, [NH(CH₃)₃]₄In₄S₁₀H₄ (1), (NH₃)₄Ga₄S₆ (2), [NH₃CH₂CH₃]₅(NH₂CH₂CH₃)₂Ga₁₁S₁₉ (3), and [NH₃CH₂CH₂OH]₆Ga₁₀S₁₈·2NH₂CH₂CH₂OH (4). All four compounds were solvothermally synthesized in mixed amine-ethanol solutions or deep eutectic solvent (DES), where ammonia/amine molecules play significant structure-directing roles in the speciation and crystal growth. (1) Being protonated, the trimethylamine and ethanolamine molecules surround the T2-[In₄S₁₀H₄]^4- clusters (for 1) and [Ga₁₀S₁₈]⁶ open framework (for 4), respectively, compensating for the negative charge of the inorganic moieties. (2) With the lone pair of electrons, the ammonia molecules in 2 coordinate directly to corner Ga³⁺ ions of the {Ga₄S₆} cage to give a neutral T2-(NH₃)₄Ga₄S₆ cluster. (3) For compound 3, part of the ethylamine molecules act as terminating ligands for the T1 and T3 units in the [Ga₁₁S₁₉(NH₂CH₂CH₃)₂]⁵ layer, while the rest act as interlamellar countercations upon protonation. Theoretical studies reveal the contributions of N, C, and H to the density of states (DOS) for 2 and 3 because of their hybrid structures that combine the ammonia/amine ligands with sulfide moieties together.