title: Electronic circular dichroism in the 4f-4f transitions of a series of cesium tetrakis (+)-3-heptafluorobutyrylcamphorate Ln(III) complexes.
abstract: For electronic circular dichroism in the 4f-4f transitions (4f-4f CD) of a series of nine tetrakis ((+)-3-heptafluorobutyrylcamphorato) Ln(III) complexes, Δ-SAPR-8-C(4)(llll) Cs[Ln((+)-hfbc)(4)]·H(2)O (Cs-Ln = Cs-Pr, -Nd, -Sm, -Eu, -Dy, -Ho, -Er, -Tm, -Yb), the spectroscopic observables such as the dissymmetry factor g = Δε/ε values with the intensities (Δε) of the CD components and the molar absorption intensities (ε) in the 4f-4f transitions between the (2S+1)L(J) levels are compared with each other to test the classification of the CD components in the relative order of the observables predicted in terms of the selection rule for 4f-4f transitions. The 4f-4f CD-based chiroptical spectra-structural relationship across the series of Δ-SAPR-8-C(4)(llll) lanthanide(III) complexes is proposed: the signs of the 4f-4f CD or CPL in the hypersensitive transitions are related to the absolute configuration; Ln complexes with a negative CD component have the Δ-configuration around Ln(III) and vice versa.
authors: Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043, Japan.
authors: Dai
authors: D
authors: Shirotani
authors: Hisako
authors: H
authors: Sato
authors: Kazuaki
authors: K
authors: Yamanari
authors: Sumio
authors: S
authors: Kaizaki
mesh_terms: D002586:Cesium / Q000737:chemistry*; D002942:Circular Dichroism; D056831:Coordination Complexes / Q000737:chemistry*; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D008968:Molecular Conformation
chemical_list: D056831:Coordination Complexes; D028581:Lanthanoid Series Elements; D002586:Cesium