Abstract
The 2,2,6,6-tetramethylpiperidine nitroxide radical (TMPN) was studied by EPR and electronic absorption spectroscopy in LiClO4 solutions in various organic solvents. The14N hyperfine structure, together with the exchange broadening of its components in EPR and the electronic n→π* transition in the visible region, provide useful information about Li+-TMPN complexes. Both spectroscopic methods prove that the oxygen atom of TMPN was involved in the Li+-TMPN interaction. The complex formation constants 15.61, 2.50, 0.75, 0.61, 0.75, and 0.33 dm3-mol−1 were found in nitromethane, benzonitrile, acetonitrile, propylene carbonate, acetone and tetrahydrofurane, respectively. These formation constants were correlated with donor and acceptor numbers of the solvents and interpreted in terms of competitive Li+-TMPN, solvent-Li+, and solvent-TMPN interactions.
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Kołodziejski, W. Paramagnetic probe for molecular interactions: I. EPR and electronic absorption studies of lithium cation solvation by a nitroxide radical. J Solution Chem 15, 597–610 (1986). https://doi.org/10.1007/BF00645813
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DOI: https://doi.org/10.1007/BF00645813