Ionic liquids and deep eutectic mixtures as new solvents for the synthesis of vanadium fluorides and oxyfluorides

Abstract

An exploratory study of the synthesis of vanadium (oxy)fluorides (VOFs) using ionic liquids (ILs) and deep eutectic mixtures (DESs) as a solvent yielded 10 different materials. The previously reported chain type: (NH₄)₂VF₅ (1), (NH₄)₂VOF₄ (2), NH₄VO₃ (3) and (H₂NH₂(CH₂)₂NH₂)VF₅ (9) have been successfully produced for the first time using ILs as the reaction media. The monomeric (HNH₂CH₃)₂VOF₄(H₂O) (4), the dimer (HNH₂CH₃)₄V₂O₂F₈ (5) and the 1D chains (HNH₂CH₃)₂VF₅ (6), (H₂O)₂VF₃ (7), α-(H₂NH₂(CH₂)₂NH₂)VOF₄ (8) and β-(H₂NH₂(CH₂)₂NH₂)VOF₄ (10) are novel materials. Template control has also been achieved by the selective choice of ILs or the appropriate deep eutectic mixture, where the expected template is delivered to the reaction by the partial breakdown of the urea derivative portion of the DES.