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The current interest in functionalized calixarenes with phosphorylated pendant arms resides in their coordination ability towards  f  elements and capability towards actinide/rare earth separation. Uranyl cation forms 1:1 and 1:2 (M:L) complexes with a tetra-phosphinoylated  p-tert -butylcalix[4]arene, B 4 bL 4 : UO 2 (NO 3 ) 2 (B 4 bL 4 )  n  ·  x H 2 O ( n  = 1,  x  = 2,  1 ;  n  = 2,  x  = 6,  2 ). Spectroscopic data point to the inner coordination sphere of  1  containing one monodentate nitrate anion, one water molecule and the four phosphinoylated arms bound to UO 2  2+  while in  2 , uranyl is only coordinated to calixarene ligands. In both cases the U(VI) ion is 8-coordinate. Uranyl complexes display enhanced metal-centred luminescence due to energy transfer from the calixarene ligands; the luminescence decays are bi-exponential with associated lifetimes in the ranges 220 μs &lt; τ  s  &lt;250 μs and 630 μs &lt; τ  L  &lt; 640 μs, pointing to the presence of two species with differently coordinated calixarene, as substantiated by a XPS study of U(4 f  5/2,7/2 ), O(1 s ) and P(2 p ) levels on solid state samples. The extraction study of UO 2  2+  cation and trivalent rare-earth (Y, La, Eu) ions from acidic nitrate media by B 4 bL 4  in chloroform shows the uranyl cation being much more extracted than rare earths.

Uranyl complexes formed with a para-t -butylcalix[4]arene bearing phosphinoyl pendant arms on the lower rim. Solid and solution studies