Preparation and Spectroscopic, Magnetic, and Electrochemical Studies of Mono-/Biradical TEMPO Derivatives
2013
A comparison set of mono-/biradical TEMPO derivatives was prepared, novel compounds were fully characterized, and their physicochemical properties were determined. Cyclic voltammetry revealed reversible redox behavior for all studied nitroxides. Moreover, the electron- withdrawing substituents increased the oxidation potential of the respective nitroxides in comparison to electron-donating groups. While EPR spectra of monoradicals in dichloromethane at 295 K reveal the expected three-line signal, spectra of biradicals show more complex features. DFT and MP2 calculations indicate that the EPR splitting pattern of dinitroxide 7 could be explained by its interactions with solvent molecules. In the solid state, mononitroxides 4 and 5 behave as a Heisenberg antiferromagnetic chain, whereas dinitroxides 6−8 are almost isolated paramagnetic diradicals coupled in an antiferromagnetic manner.
Keywords:
- Correction
- Source
- Cite
- Save
- Machine Reading By IdeaReader
42
References
14
Citations
NaN
KQI