CHARGE-TRANSFER ASSOCIATION AND PARAMAGNETISM OF SOME ORGANIC SYSTEMS
When p-xylene was combined with chloranil in n-heptane, charge-transfer optical absorption was observed. The magnitude of this absorption was used to calculate an equilibrium constant for the formation of a donor-acceptor complex containing one p-xylene was combined with carbon tetrabromide and with carbon tetrachloride in n-heptane, no charge-transfer absorption was observed. Reactions of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) with chloranil (pQCl/ sub 4/) were observed in ethylene dichloride and acetonitrile. In both solvents adduct formation occurred initially, as observed by its charge-transfer absorption. In acetonitrile time-dependent electron spin resonance (ESR) absorption was observed, and it was identified with the positive and negative radical ions of TMPD and pQCl/sub 4/, respectively. In this case a completely ionized electron transfer had occurred. Chloranil and other quinones were found to react with N,N-dimethylaniline forming a crystal violet salt. The diamagnetic donor-acceptor complexes and also semiquinone radicals are intermediates which were observed. Some physical measurements of the kinetics of this reaction are described and correlated. When fluoranil was allowed to react with dimethylaniline, the hyperfine splitting by the fluorine atoms of the fluoranil radical was not resolved. Characteristics of the ESR absorption by this radical in dimethylaniline are discussed in terms of an electron transfer between the semiquinone and quinone, and between the semiquinone and hydroquinone ion. Paramagnetism was discovered in hydrocarbon-quinone solids. ESR absorption was assigned to imperfections in the solid which was normally diamagnetic. The preparation of these solids and some of their physical characteristics are described. (auth)
- Research Organization:
- University of California, Lawrence Radiation Laboratory, Berkeley, CA (US)
- Sponsoring Organization:
- US Atomic Energy Commission (AEC)
- DOE Contract Number:
- W-7405-ENG-48
- NSA Number:
- NSA-15-029098
- OSTI ID:
- 4843102
- Report Number(s):
- UCRL-9722
- Resource Relation:
- Other Information: Orig. Receipt Date: 31-DEC-61
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ABSORPTION
ALKANES
AMINES
AROMATIC HYDROCARBONS
AROMATICS
ATOMS
CARBON TETRACHLORIDE
CHEMICAL REACTIONS
CHLORANIL
CHLORINE COMPOUNDS
ELECTRONS
FLUORINE
HYDROCARBONS
HYPERFINE STRUCTURE
ISOMERS
MAGNETISM
MEASURED VALUES
METHYL RADICALS
NITROGEN COMPOUNDS
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
PHENYL RADICALS
QUINONES
REACTION KINETICS
RESONANCE
SPIN
XYLENE
XYLENE-PARA