Fluorinated β-Diketones for the Extraction of Lanthanide Ions: Photophysical Properties and Hydration Numbers of Their EuIII Complexes
Tris(β-diketonato)europium(III) with a series of variably fluorinated ligands derived from 3,5-heptanedione were synthesised with the aim of determining their hydration state under extraction conditions. The number of coordinated water molecules was determined by measuring the lifetime of the Eu(5D0) excited level in water and deuterated water. The hydration gain (Δq = q – q0) after shaking chloroform solutions during 10 min with 0.1 M NaClO4 aqueous solutions depends on the fluorination extent of the diketonates: fluorination of one methyl group leads to a decrease in Δq of ca. 0.5 unit, while fluorination of one ethyl group results in a decrease of ca. 1.3 units. Highly fluorinated complexes (i.e with hexafluoroacetylacetonate and related ligands) display a hydration number close to one while poorly fluorinated compounds (or nonfluorinated ones, such as the acetylacetonate complex) have a hydration state close to two. Photophysical properties of the EuIII β-diketonates are also described and the synthesis of the fluorinated β-diketones is re-investigated and discussed in details.