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We have synthesized a series of novel functionalized phosphine oxides: [2-FG-(CH2)nOC6H4]3PO (FG = Ph2P(O), CO2H, tetrazol-1-yl, 3-Ph-triazol-5-yl; n = 1, 3), promising as receptors and ligands for applications in catalysis, biomedicine, designing molecular containers, etc. For the first time, we revealed the formation of atrane-type lanthanide complexes with tetradentate coordination of the ligands in solutions.