4.7 Article

Electronic circular dichroism in the 4f-4f transitions of a series of cesium tetrakis (+)-3-heptafluorobutyrylcamphorate Ln(III) complexes

Journal

DALTON TRANSACTIONS
Volume 41, Issue 35, Pages 10557-10567

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c2dt30951c

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For electronic circular dichroism in the 4f-4f transitions (4f-4f CD) of a series of nine tetrakis ((+)-3-heptafluorobutyrylcamphorato) Ln(III) complexes,Delta-SAPR-8-C-4(llll) Cs[Ln((+)-hfbc)(4)]center dot H2O (Cs-Ln = Cs-Pr, -Nd, -Sm, -Eu, -Dy, -Ho, -Er, -Tm, -Yb), the spectroscopic observables such as the dissymmetry factor g = Delta epsilon/epsilon values with the intensities (Delta epsilon) of the CD components and the molar absorption intensities (epsilon) in the 4f-4f transitions between the L-2S+1(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 Delta-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 Delta-configuration around Ln(III) and vice versa.

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