A ligand system containing three carbamoylmethylphosphine oxide (CMPO) moieties attached to a tripodal platform with a central nitrogen atom has been synthesized for metal complexation and extraction from neutral and nitric acid solutions. Liquid-liquid extractions performed for Ln(III), both from neutral and acidic media, show excellent extraction properties which exceeded those for the known mono- and di-CMPO derivatives as well as the related tripodands. A considerable enhancement of the DLn values was observed in the presence of IL ([bmim][Tf2N]) in the organic phase towards lanthanide ions from 3M HNO3 solutions. The protonation of the central amine nitrogen atom of the ligand 1 in the acidic media provides also the effective extraction of the perrhenate anionic complexes. The europium complexes formed by mono- and tris-CMPO ligands in the solid state, as well as Eu(III) and Tb(III) complexes generated in solutions, possess intensive luminescence at 300K
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