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

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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
Issue number19
Publication statusPublished - Oct 7 2003
Externally publishedYes


ASJC Scopus subject areas

  • Chemistry(all)

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