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The2 E↔4 A 2 transition in tetragonal Cr3+ complexes

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Abstract

The2 E↔4 A 2 absorption and emission spectra of [Cr(NH3)5(NO3)](NO3)2, [Cr(NH3)5(NO2)] ·(NO3)2, and [Cr(NH3)5(H2O)](NO3)3 microcrystals have been recorded at 77°K. Tetragonal2E splittings are 209, 188 and 87 cm−1, respectively. An analysis of the limited vibronic structure has been made and compared to the results for the parent “octahedral” complex, [Cr(NH3)6](NO3)3. Vibrations of approximately 270 and 700 cm−1 are prominent.

Zusammenfassung

Die2 E↔4 A 2 Absorptions- und Emissionsspektren von [Cr(NH3)5(NO3)](NO3)2-, [Cr(NH3)5 (NO2)](NO3)2- und [Cr(NH3)5(H2O)](NO3)3-Mikrokristallen werden für 77° angegeben. Die tetragonalen2 E Aufspaltungen sind209, 188 bzw. 87 cm−1. Eine Analyse der begrenzten vibronischen Struktur wurde vorgenommen und mit den Resultaten für den oktaedrischen Stammkomplex, [Cr(NH3)6](NO3)3 verglichen. Schwingungen von etwa 270 und 700 cm−1 treten besonders hervor.

Résumé

Les spectres d'émission et d'absorption2 E↔4 A 2 de microcristaux de [Cr(NH3)5(NO3)](NO3)2, [Cr(NH3)5(NO2)](NO3)2 et [Cr(NH3)5(H2O)](NO3)3 ont été enregistrés à 77° K. Les écartements tétragonaux2 E sont respectivement 209, 188 et 87 cm−1. Une analyse de la structure vibronique limitée a été effectuée et comparée aux résultats pour le complexe ≪octaédral≫ parent [Cr(NH3)6](NO3)3. Les vibrations au voisinage de 270 et 700 cm−1 émergent.

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Authors and Affiliations

  1. Department of Chemistry, the University of Arizona, 85721, Tucson, Arizona

    Whiting N. Shepard & Leslie S. Forster

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  1. Whiting N. Shepard
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  2. Leslie S. Forster
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This contribution is dedicated to the memory of Prof. Hans-Ludwig Schläfer, a stimulating colleague and valued friend.

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Shepard, W.N., Forster, L.S. The2 E↔4 A 2 transition in tetragonal Cr3+ complexes. Theoret. Chim. Acta 20, 135–142 (1971). https://doi.org/10.1007/BF00569260

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