Abstract

AbstractDistorted coordination structures and luminescence properties of novel lanthanide complexes with oxo-linked bidentate phosphane oxide ligands, 4,5-bis(diphenylphosphoryl)-9,9-dimethylxanthene (xantpo), 4,5-bis(di-tert-butylphosphoryl)-9,9-dimethylxanthene (tBu-xantpo) and bis[(2-diphenylphosphoryl)phenyl]ether (dpepo) and low-vibrational frequency hexafluoroacetylacetonato (hfa) ligands are reported. The lanthanide complexes exhibit characteristic square antiprism and trigonal dodecahedron structures with octa-coordinated oxygen atoms. The luminescence properties of these complexes are characterized by their emission quantum yields, emission lifetimes, and their radiative and non-radiative rate constants. Lanthanide complexes with dodecahedron structures offer markedly high emission quantum yields (Eu: 55–72 %, Sm: 2.4–5.0 % in acetone-d 6) due to enhancement of the electric dipole transition and suppression of vibrational relaxation. These remarkable luminescence properties are elucidated in terms of their distorted coordination structures.KeywordsSamariumCoordination structureDodecahedronAsymmetryShape measure

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