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

被引:27
|
作者
Shirotani, Dai [1 ,2 ]
Sato, Hisako [3 ]
Yamanari, Kazuaki [2 ]
Kaizaki, Sumio [1 ,4 ]
机构
[1] Osaka Univ, Dept Chem, Grad Sch Sci, Toyonaka, Osaka 5600043, Japan
[2] Osaka Univ, Inst Higher Educ Res & Practice, Toyonaka, Osaka 5600043, Japan
[3] Ehime Univ, Dept Chem, Fac Sci, Matsuyama, Ehime 7908577, Japan
[4] Osaka Univ, Venture Business Lab, Suita, Osaka 5650871, Japan
关键词
CHIRAL LANTHANIDE COMPLEXES; POLARIZED LUMINESCENCE; OPTICAL-ACTIVITY; CRYSTAL-STRUCTURE; ADDUCT FORMATION; SINGLE-CRYSTAL; ABSORPTION; LIGANDS; SPECTRA; LN;
D O I
10.1039/c2dt30951c
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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.
引用
收藏
页码:10557 / 10567
页数:11
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