Behavior of Nitroxide Biradicals with Acetylene Bridges in Organic Solvents and Ionic Liquids

Intramolecular electron spin exchange (IESE) in two nitroxide biradicals, R 6 –C≡C–C≡C–R 6 ( 1 ) and R 6 –C≡C– p -C 6 H 4 –C≡C–R 6 ( 2 ), is studied as a function of temperature and solvent properties. The effect of molecular solvents and ionic liquids (ILs, [1-methyl-3-butylimidazolium] + [PF 6 ] −...

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Bibliographic Details
Published in:Applied magnetic resonance 2013-09, Vol.44 (9), p.1041-1051
Main Authors: Kokorin, A. I., Golubeva, E. N., Mladenova, B. Y., Tran, V. A., Kálai, T., Hideg, K., Grampp, G.
Format: Article
Language:English
Subjects:
Acetylene
Atoms and Molecules in Strong Fields
Electron paramagnetic resonance
Electron spin
Electrons
Ethanol
Geometry
Ionic liquids
Laser Matter Interaction
Mathematical analysis
Organic Chemistry
Physical Chemistry
Physics
Physics and Astronomy
Solid State Physics
Solvents
Spectroscopy/Spectrometry
Spin exchange
Temperature
Tensors
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Summary:Intramolecular electron spin exchange (IESE) in two nitroxide biradicals, R 6 –C≡C–C≡C–R 6 ( 1 ) and R 6 –C≡C– p -C 6 H 4 –C≡C–R 6 ( 2 ), is studied as a function of temperature and solvent properties. The effect of molecular solvents and ionic liquids (ILs, [1-methyl-3-butylimidazolium] + [PF 6 ] − , bmimPF 6 , and [1-methyl-3-octylimidazolium] + [BF 4 ] − , omimBF 4 ) on the IESE in magnetically diluted solutions is investigated. Changes in electron paramagnetic resonance spectra are analyzed and the thermodynamic parameters of these changes are calculated. Geometry optimization and D -tensor calculations of biradicals 1 and 2 were carried out on the DFT/UB3LYP/cc-pVdz and DFT/ROPBE/N07D levels of theory. The probable differences in biradical behavior are discussed.
ISSN:0937-9347
1613-7507
DOI:10.1007/s00723-013-0459-5