TY - JOUR
T1 - 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
AU - Subhan, Md Abdus
AU - Suzuki, Takayoshi
AU - Fuyuhiro, Akira
AU - Kaizaki, Sumio
PY - 2003/9/25
Y1 - 2003/9/25
N2 - 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.
AB - 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.
KW - Chirality
KW - Coordination chemistry
KW - Intramolecular interactions
KW - Lanthanides
KW - X-ray diffraction, X-ray powder diffraction
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U2 - 10.1039/b304928k
DO - 10.1039/b304928k
M3 - Article
AN - SCOPUS:0142258766
VL - 3
SP - 3785
EP - 3791
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 19
ER -