Issue 4, 2001

Stereospecific assembly of chiral Λ-Cr(III)-Δ-Ln(III)-oxalato-bridged dinuclear 3d–4f complexes (Ln = Yb or Dy) and near infrared circular dichroism in the 4f→4f transitions

Abstract

Stereospecific formation of the chiral heterodinuclear 3d–4f complexes (Λ–Δ)-[(acac)2Cr(ox)Ln(HBpz3)2] (acac = acetylacetonate, ox2− = oxalato, HBpz3 = hydrotris(pyrazol-1-yl)borato; Ln = Yb: 1, Dy: 2 where (Λ–Δ) implies the absolute configuration around the octahedral Cr and square antiprismatic Ln moiety, respectively) was demonstrated by comparing the near infrared circular dichroism (NIR CD) in the 4f→4f transitions and/or the single crystal X-ray analysis with those of a diastereomeric mixture of the mononuclear Λ-, and Δ-[Yb(HBpz3)2(S-pba)] 3 (S-pba = S-(+)-2-phenylbutyrate) complex. The NIR CD spectra for the 4f→4f transitions of the 3d–4f (Λ–Δ)-Cr(ox)Ln complexes 1 and 2 with configurational chirality around the Ln ion with no asymmetric carbon were observed for the first time in CH2Cl2.This observation is supported by the selection rule for the optical activity of the 4f→4f transitions. The first solution NIR magnetic circular dichroism (MCD) of the racemic Cr(ox)Yb and Cr(ox)Dy complexes is also reported.

Graphical abstract: Stereospecific assembly of chiral Λ-Cr(III)-Δ-Ln(III)-oxalato-bridged dinuclear 3d–4f complexes (Ln = Yb or Dy) and near infrared circular dichroism in the 4f→4f transitions

Supplementary files

Article information

Article type
Paper
Submitted
12 Sep 2000
Accepted
21 Dec 2000
First published
30 Jan 2001

J. Chem. Soc., Dalton Trans., 2001, 492-497

Stereospecific assembly of chiral Λ-Cr(III)-Δ-Ln(III)-oxalato-bridged dinuclear 3d–4f complexes (Ln = Yb or Dy) and near infrared circular dichroism in the 4f→4f transitions

Md. A. Subhan, T. Suzuki and S. Kaizaki, J. Chem. Soc., Dalton Trans., 2001, 492 DOI: 10.1039/B007369P

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