The electronic structure and spectra of spin-triplet ground state bis(biuretato)cobalt(iii) coordination compounds

Peter W. Thulstrup; Erik Larsen

doi:10.1039/b513571k

The electronic structure and spectra of spin-triplet ground state bis(biuretato)cobalt(iii) coordination compounds

Peter W. Thulstrup^*, Erik Larsen

^*Corresponding author for this work

Department of Chemistry

1 Citation (Scopus)

Abstract

The planar coordination compounds of cobalt(iii) with bis(biuretato) ligands are highly unusual due to their intermediate spin triplet ground state. Density functional theory (DFT) and time-dependent DFT have been applied in a study of the structure and electronic spectroscopy of this type of coordination compounds. The investigations included prediction and spectroscopic measurements of the absorption and circular dichroism (CD), as well as an experimental study of the magnetic CD. The results obtained by TD-DFT were in excellent agreement with the observed spectral features, both regarding the d–d and the charge transfer regions. There was noted a systematic blue-shift of the TD-DFT results compared to experiment, corresponding to an offset of ca. 0.5 µm⁻¹and a scaling factor of 1.25 for the transition energies. The DFT results are rationalized in terms of a qualitative MO analysis.

Original language	English
Journal	Journal of the Chemical Society. Dalton Transactions
Volume	60
Issue number	1414
Pages (from-to)	17841784-17891789
Number of pages	50,006
ISSN	1477-9226
DOIs	https://doi.org/10.1039/b513571k
Publication status	Published - 27 Mar 2006

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title = "The electronic structure and spectra of spin-triplet ground state bis(biuretato)cobalt(iii) coordination compounds",

abstract = "The planar coordination compounds of cobalt(iii) with bis(biuretato) ligands are highly unusual due to their intermediate spin triplet ground state. Density functional theory (DFT) and time-dependent DFT have been applied in a study of the structure and electronic spectroscopy of this type of coordination compounds. The investigations included prediction and spectroscopic measurements of the absorption and circular dichroism (CD), as well as an experimental study of the magnetic CD. The results obtained by TD-DFT were in excellent agreement with the observed spectral features, both regarding the d–d and the charge transfer regions. There was noted a systematic blue-shift of the TD-DFT results compared to experiment, corresponding to an offset of ca. 0.5 µm−1and a scaling factor of 1.25 for the transition energies. The DFT results are rationalized in terms of a qualitative MO analysis.",

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T1 - The electronic structure and spectra of spin-triplet ground state bis(biuretato)cobalt(iii) coordination compounds

AU - Thulstrup, Peter W.

AU - Larsen, Erik

PY - 2006/3/27

Y1 - 2006/3/27

N2 - The planar coordination compounds of cobalt(iii) with bis(biuretato) ligands are highly unusual due to their intermediate spin triplet ground state. Density functional theory (DFT) and time-dependent DFT have been applied in a study of the structure and electronic spectroscopy of this type of coordination compounds. The investigations included prediction and spectroscopic measurements of the absorption and circular dichroism (CD), as well as an experimental study of the magnetic CD. The results obtained by TD-DFT were in excellent agreement with the observed spectral features, both regarding the d–d and the charge transfer regions. There was noted a systematic blue-shift of the TD-DFT results compared to experiment, corresponding to an offset of ca. 0.5 µm−1and a scaling factor of 1.25 for the transition energies. The DFT results are rationalized in terms of a qualitative MO analysis.

AB - The planar coordination compounds of cobalt(iii) with bis(biuretato) ligands are highly unusual due to their intermediate spin triplet ground state. Density functional theory (DFT) and time-dependent DFT have been applied in a study of the structure and electronic spectroscopy of this type of coordination compounds. The investigations included prediction and spectroscopic measurements of the absorption and circular dichroism (CD), as well as an experimental study of the magnetic CD. The results obtained by TD-DFT were in excellent agreement with the observed spectral features, both regarding the d–d and the charge transfer regions. There was noted a systematic blue-shift of the TD-DFT results compared to experiment, corresponding to an offset of ca. 0.5 µm−1and a scaling factor of 1.25 for the transition energies. The DFT results are rationalized in terms of a qualitative MO analysis.

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U2 - 10.1039/b513571k

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M3 - Journal article

AN - SCOPUS:85034353388

SN - 1472-7773

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JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 1414

ER -

The electronic structure and spectra of spin-triplet ground state bis(biuretato)cobalt(iii) coordination compounds

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