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

TY - JOUR

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.

UR - http://www.scopus.com/inward/record.url?scp=85034353388&partnerID=8YFLogxK

U2 - 10.1039/b513571k

DO - 10.1039/b513571k

M3 - Journal article

AN - SCOPUS:85034353388

SN - 1477-9226

VL - 60

SP - 17841784

EP - 17891789

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

IS - 1414

ER -