Spectroscopic Effects of Excited-State Coupling in a Tetragonal Chromium(III) Complex

Detailed low-temperature single-crystal polarized absorption and luminescence spectra of Cs2[CrCl2(H 2O)4]Cl3 are reported. The luminescence spectrum is a broad band with a maximum at 11 800 cm −1, indicating that the trans-[CrCl2(H2O)4]+ complex emits from a quartet excited state. The resolved vibr...

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Bibliographic Details
Published in:Inorganic chemistry 2008-06, Vol.47 (12), p.5048-5054
Main Authors: Beaulac, Rémi, Reber, Christian
Format: Article
Language:English
Subjects:
Absorption spectra
Electronics
Emittance
Excitation spectra
Luminescence
Origins
Spectra
Spectroscopy
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Summary:Detailed low-temperature single-crystal polarized absorption and luminescence spectra of Cs2[CrCl2(H 2O)4]Cl3 are reported. The luminescence spectrum is a broad band with a maximum at 11 800 cm −1, indicating that the trans-[CrCl2(H2O)4]+ complex emits from a quartet excited state. The resolved vibronic structure reveals a progression in a nontotally symmetric 445 cm−1 b1g mode, a manifestation of a Jahn−Teller effect in the emitting state. The absorption spectrum shows completely linearly polarized, magnetic-dipole-allowed electronic origins, defining the tetragonal splitting of the states originating from 4T2g (O h ). An energy gap of approximately 800 cm−1 is observed between the electronic origins of the emitting state and the onset of the π-polarized absorption spectrum. Both Jahn−Teller and spin−orbit couplings in the orbitally degenerate 4Eg (D 4h ) state are necessary to account for the spectroscopic observations.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic702281k