The 2D composition-space diagram of the Al(OH)₃−<i>Am</i>_<i>2</i><i>TAZ</i>−HF_aq−ethanol system is established under microwave heating at 190 °C for [Al³⁺] = 1 mol·L⁻¹. Four new fluoroaluminates are evidenced when the [HF]/[<i>Am</i>_<i>2</i><i>TAZ</i>] ratio is increased in the starting solution, and the dimensionality of the inorganic frameworks is increased from 0D in [H<i>Am</i>_<i>2</i><i>TAZ</i>]₂·(AlF₅(H₂O))·2H₂O (<i>Pc</i>, <i>Z</i> = 2), to 1D in [H<i>Am</i>_<i>2</i><i>TAZ</i>]₂·(AlF₅) and [H<i>Am</i>_<i>2</i><i>TAZ</i>]₂·(Al₂F₈) (<i>Fdd</i>2, <i>Z</i> = 8), and to 2D in [H<i>Am</i>_<i>2</i><i>TAZ</i>]₂·(Al₅F₁₇) (<i>Imm</i>2, <i>Z</i> = 2). This evolution is partially paralleled by the thermal decomposition of [H<i>Am</i>_<i>2</i><i>TAZ</i>]₂·(AlF₅(H₂O))·2H₂O; on heating, this hydrate gives [H<i>Am</i>_<i>2</i><i>TAZ</i>]₂·(AlF₅) at 100−150 °C and [H<i>Am</i>_<i>2</i><i>TAZ</i>]₂·(Al₂F₈) at 180 °C; the loss and simultaneous decomposition of [H<i>Am</i>_<i>2</i><i>TAZ</i>]F leave a solid residue of polymeric paracyanogen (CN)_2<i>n</i> that is further decomposed and hydrolyzed into HCN and HNCO by atmospheric water traces. NMR ¹⁹F spectroscopy of [H<i>Am</i>_<i>2</i><i>TAZ</i>]₂·(AlF₅) is in agreement with the crystallographic determination, and the ²⁷Al spectrum demonstrates that a significant F⁻/OH⁻ substitution is excluded.< Réduire