Electronic circular dichroism in the 4f-4f transitions of a series of cesium tetrakis (+)-3-heptafluorobutyrylcamphorate Ln(III) complexes
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...
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Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2012-09, Vol.41 (35), p.10557-10567 |
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Sprache: | eng |
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Zusammenfassung: | 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. |
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ISSN: | 1477-9226 1477-9234 |
DOI: | 10.1039/c2dt30951c |