Synthesis of a para-tert-octylcalix[4]arene fitted with phosphinoyl pendant arms and its complexation properties towards f-elements

摘要: Abstract A new functionalised calixarene, para-tert-octylcalix[4]arene, fitted with phosphinoyl pendant arms (B4boctL4) 1, was synthesised and fully characterised. The procedure using xylene via a Williamson reaction between the tetra sodium derivative of calixarene dimethyl-chloromethyl-phosphine oxide decreased time from 96 to 15 h increased yield 46% 89% respect reported toluene for synthesis phosphinoylated para-tert-butyl substituents. Spectrophotometric titrations B4boctL4 La(III), Lu(III), Th(IV) UO22+ luminescence Tb(III) were performed in CH3CN presence 0.01 M (CH3CH2)4NCl. results suggest formation two predominant species 1:1 1:2 metal:ligand ratios. former had log β11 values 8.4 4.5 La(III) ions, respectively, latter β12 13.8 7.4, respectively. Based on this result, 1 M:2 L molar ratio used aim isolating Eu(III) complexes stoichiometry. However, characterisation indicated 1 M:1 L properties, such as emission excitation spectra, lifetimes quantum yields, (2) (3) isolated analysed. molecular modelling europium complex molecule based experimental suggested coordination number equal 9 distorted tri-capped trigonal prismatic geometry most probable structure. extraction ability titled CHCl3 towards UO22+, Th(IV), ions 1 M HNO3/3.5 M NaNO3 aqueous medium investigated. Tributylphosphate (TBP) (2.4 × 10−4 M) added ligand (v/v) both caused significant synergistic effect uranyl extraction, increasing 48% 96%. Under our conditions, TBP extracted only 11%. capability loading capacity Th (IV) studied.