Paramagnetic probe for molecular interactions: I. EPR and electronic absorption studies of lithium cation solvation by a nitroxide radical
The 2,2,6,6-tetramethylpiperidine nitroxide radical (TMPN) was studied by EPR and electronic absorption spectroscopy in LiClO/sub 4/ solutions in various organic solvents. The /sup 14/N hyperfine structure, together with the exchange broadening of its components in EPR and the electronic n..--> pi.. transition in the visible region, provide useful information about Li/sup +/-TMPN complexes. Both spectroscopic methods prove that the oxygen atom of TMPN was involved in the Li/sup +/-TMPN interaction. The complex formation constants 15.61, 2.50, 0.75, 0.61, 0.75, and 0.33 dm/sup 3/-mol/sup -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/sup +/-TMPN, solvent-Li/sup +/, and solvent-TMPN interactions.
- Research Organization:
- Univ. of Warsaw, Warsaw
- OSTI ID:
- 7170113
- Journal Information:
- J. Solution Chem.; (United States), Vol. 15:7
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
LITHIUM COMPOUNDS
SOLVATION
NITROGEN 14
HYPERFINE STRUCTURE
NITROXYL RADICALS
ABSORPTION SPECTRA
ELECTRON SPIN RESONANCE
BINDING ENERGY
CARBONIC ACID ESTERS
COMPLEXOMETRY
ELECTROLYTES
ELECTRONS
LITHIUM PERCHLORATES
NITRILES
NITROMETHANE
TETRAHYDROFURAN
ALKALI METAL COMPOUNDS
CHEMICAL EXPLOSIVES
CHLORINE COMPOUNDS
ELEMENTARY PARTICLES
ENERGY
ESTERS
EXPLOSIVES
FERMIONS
FURANS
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
ISOTOPES
LEPTONS
LIGHT NUCLEI
MAGNETIC RESONANCE
NITRO COMPOUNDS
NITROGEN ISOTOPES
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
PERCHLORATES
RADICALS
RESONANCE
SPECTRA
STABLE ISOTOPES
400201* - Chemical & Physicochemical Properties
640302 - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory