Chiral Dinuclear EuIII, TbIII, and YIII Complexes Supported by P‐Stereogenic Linear Tetraphosphine Tetraoxide. Issue 8 (3rd January 2022)

• Record Type: Journal Article
• Authors: Tanase, Tomoaki; Nakamae, Kanako; Okawa, Yume; Hamada, Mami; Matsumoto, Arimasa; Nakajima, Takayuki; Nakashima, Takuya; Kawai, Tsuyoshi
• Is Part Of: Chemistry. Volume 28:Issue 8(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-01-03
• Subjects: circularly polarized luminescence -- europium -- P-stereogenic tetraphosphine tetraoxide -- terbium -- yttrium; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.202104060
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: A P ‐stereogenic linear tetraphosphine tetraoxide, ( R, R )‐ or ( S, S )‐dpmppm(=O)4, was synthesized to prepare C 2 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. Abstract : A new P ‐stereogenic linear tetraphosphine tetraoxide, ( R, R )/( S, S )‐Ph2 P(=O)CH2 P(=O)(Ph)CH2 P(=O)(Ph)CH2 P(=O)Ph2 abbreviated as ( R, R )/( S, S )‐dpmppm(=O)4 (L4 RR/SS ), was synthesized to prepare C 2 dinuclear M(hfa)3 complexes, [M2 (( R, R )/( S, S )‐dpmppm(=O)4 )(hfa)6 ] (M=Y, Eu, Tb: M2 L4 RR/SS ), which revealed significant chiral induction from the P ‐chiral centers on the achiral M(hfa)3 units through intramolecular π‐π stacking constraint in the dinuclear system on the basis of circular dichroism (CD) and circularly polarized luminescence (CPL) measurements.