Trends in the Series of Ammine Rare-Earth-Metal Borohydrides: Relating Structural and Thermal Properties

Ammine metal borohydrides display extreme structural and compositional diversity and show potential applications for solid-state hydrogen and ammonia storage and as solid-state electrolytes. Thirty-two new compounds are reported in this work, and trends in the full series of ammine rare-earth-metal borohydrides are discussed. The majority of the rare-earth metals (RE) form trivalent RE­(BH₄)₃·xNH₃ (x = 7–1) compounds, which possess an intriguing crystal chemistry changing with the number of ammonia ligands, varying from structures built from complex ions (x = 5–7), to molecular structures (x = 3, 4), one-dimensional chains (x = 2), and structures built from two-dimensional layers (x = 1). Divalent RE­(BH₄)₂·xNH₃ (x = 4, 2, 1) compounds are observed for RE²⁺ = Sm, Eu, Yb, with structures varying from molecular structures (x = 4) to two-dimensional layered (x = 2, 1) and three-dimensional structures (Yb­(BH₄)₂·NH₃). The crystal structure and composition of the compounds depend on the volume of the rare-earth ion. In all structures, NH₃ coordinates to the metal, while BH₄^– has a more flexible coordination and is observed as a bridging and terminal ligand and as a counterion. RE­(BH₄)₃·xNH₃ (x = 7–5, 4) releases NH₃ stepwise during thermal treatment, while mainly H₂ is released for x ≤ 3. In contrast, only NH₃ is released from RE­(BH₄)₂·xNH₃ due to the lower charge density on the RE²⁺ ion and higher stability of RE­(BH₄)₂. The thermal stability of RE­(BH₄)₃·xNH₃ increase with increasing cation charge density for x = 5, 7, while it decreases for x = 4, 6. For x = 3, the thermal stability decreases with increasing charge density, due to the destabilization of the BH₄^– group, making it more reactive toward NH₃. This research provides a large number of novel compounds and new insight into trends in the crystal chemistry of ammine metal borohydrides and reveals a correlation between the local metal coordination and the thermal stability.