Publication
Title
Vibrational circular dichroism spectroscopy of a spin-triplet bis-(biuretato) cobaltate(III) coordination compound with low-lying electronic transitions
Author
Abstract
Vibrational absorption (VA) and vibrational circular dichroism (VCD) spectroscopy was applied in the analysis of vibrational and low lying electronic transitions of a triplet ground state cobalt(III) coordination compound. The spectroscopic measurements were performed on the tetrabutylammonium salt of (6S, 7S)-1,3,5,8,10,12-hexaaza-2,4,9,11-tetraoxo-6,7-diphenyl-dodecanato(4-) cobaltate( III) in DMSO solution and in potassium bromide pellets. The chiral anion exhibits an unusual geometry for cobalt( III), being four-coordinate, planar, and paramagnetic with an intermediate spin state. The spectroscopic results were compared to measurements performed on the free ligand and to theoretical calculations using density functional theory (B3LYP/TZVP). The results of the VCD analysis of the coordination compound identified an electronic, dipole-forbidden, magnetic dipole-allowed low-lying d-d transition located in the mid infrared, as well as several amide stretch transitions located in the fingerprint region (1800-1100 cm(-1)), in both the liquid and solid phase. VCD signals were found to be 5-10 times higher than expected, indicating enhancement of the vibrational CD signals, caused by coupling of the vibrational transitions with the close-lying electronic transition.
Language
English
Source (journal)
Journal of the Chemical Society: Dalton transactions. - London
Publication
London : 2007
ISSN
0300-9246
1477-9226
1472-7773
Volume/pages
10(2007), p. 1028-1033
ISI
000244487800005
Full text (Publisher's DOI)
UAntwerpen
Faculty/Department
Publication type
Subject
External links
Web of Science
Record
Identification
Creation 20.12.2013
Last edited 03.11.2017