Chiral Dinuclear EuIII , TbIII , and YIII Complexes Supported by P-Stereogenic Linear Tetraphosphine Tetraoxide

Abstract

A P-stereogenic linear tetraphosphine tetraoxide, (R,R)- or (S,S)-dpmppm(=O)₄ , was synthesized to prepare C₂ dinuclear M(hfa)₃ complexes (M=Eu, Tb, Y) as the first example of lanthanide(III) complexes with P-chiral multidentate phosphine oxides. The mononuclear M(hfa)₃ complexes (M=Eu, Y) with a P-chiral diphosphine dioxide, tpdpb(=O)₂ , were also prepared, and comparison of their photophysical properties for the Eu^III complexes revealed that significant chiral induction from the P-chiral centers arises on the achiral M(hfa)₃ units through intramolecular π-π stacking constraint in the dinuclear system.

Keywords: P-stereogenic tetraphosphine tetraoxide; circularly polarized luminescence; europium; terbium; yttrium.