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†
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