Synthesis, X-ray structures and NIR chiroptical properties of a series of dinuclear lanthanide(iii) complexes [Ln2(μ-(S- or RS-pba))4(HBpz3)2] novel configurational chirality due to non-bonding Ln⋯O interactions

Md Abdus Subhan, Takayoshi Suzuki, Akira Fuyuhiro, Sumio Kaizaki

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)

Abstract

Two series of mononuclear [LnIII(S- or RS-pba)(HBpz3)2] (Ln = Tm, Er, Ho) and dinuclear [Ln2(μ-(S- or RS-pba))4(HBpz3−)2] (Ln = Yb, Ho, Gd, Dy, Nd) complexes (pba = RS- and/or S-2-phenyl butyrate, HBpz3 = hydrotris(pyrazol-1-yl)borate) were prepared and their X-ray structures and NIR chiroptical properties investigated. Synthesis with a molar ratio 1 ∶ 2 ∶ 1 of Ln ∶ KHBpz3 ∶ pba results in the formation of either mono- or dinuclear complexes, depending on the Ln(iii) ionic radii: mononuclear complexes from Yb(iii) to Ho(iii) and dinuclear ones from Dy(iii) to Nd(iii). Only the dinuclear complexes for all of the Ln(iii) studied were formed with a molar ratio 1 ∶ 1 ∶ 2 of Ln ∶ KHBpz3 ∶ pba. X-Ray structural analysis confirmed dinuclear structures with CH⋯π interactions and linear B⋯Ln⋯Ln⋯B arrangements for the Ln(μ-RS-pba)4Ln(HBpz3)2 (Yb, Ho, Dy, Gd and Nd) complexes and a skew bent arrangement of B⋯Ln⋯Ln⋯B leading to configurational chirality in the Dy(μ-S-pba)4Dy(HBpz3)2 complex. Comparison of NIR chiroptical spectra in the 4f–4f transitions with those of the corresponding Cr–Ln complexes, [(acac)2Cr(ox)Ln(HBpz3)2] suggests that the 4f–4f CD intensities arise from configurational chirality, probably due to the skew bent B⋯Ln⋯Ln⋯B disposition.

Original languageEnglish
Pages (from-to)3785-3791
Number of pages7
JournalJournal of the Chemical Society. Dalton Transactions
Volume3
Issue number19
DOIs
Publication statusPublished - Sep 25 2003
Externally publishedYes

Keywords

  • Chirality
  • Coordination chemistry
  • Intramolecular interactions
  • Lanthanides
  • X-ray diffraction, X-ray powder diffraction

ASJC Scopus subject areas

  • Chemistry(all)

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