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Electronic structures of ion radicals of N-heteroaromatic hydrocarbons as studied by ESR and optical spectroscopy

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00517a014· OSTI ID:5541794
;
Various N-heterosubstituted benzenes, naphthalenes, anthracenes, and phenanthrenes have been ionized to their ion radicals in frozen solutions through intermolecular charge transfer induced by ..gamma..-ray irradiation. Cation and anion radicals have been produced selectively and studied by ESR and optical spectroscopy. The cations can be grouped into those in which the spin density is localized mainly on the in-plane lone-pair orbitals of nitrogen (n cations) and those in which the density is distributed over a ..pi..-electron orbital (..pi.. cations). They can be unambiguously distinguished by ESR and optical spectra. For the n cations the optical transition energies are in accord with photoelectron spectra. The spin density of the n cations substantiates significant interactions of lone-pair orbitals as elaborated previously in terms of through-space and through-bond interactions. The ..pi.. cations and ..pi.. anions exhibit an approximate mirror image relation in the optical spectrum. Failure of CNDO/S calculations to account for the observed optical spectra of n cations suggests sigma-..pi.. interactions. 14 figures, 1 table.
Research Organization:
Kyoto Univ., Japan
OSTI ID:
5541794
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:23; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400104 -- Spectral Procedures-- (-1987)
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ANIONS
ANTHRACENE
AROMATICS
ATOMIC IONS
BENZENE
CATIONS
CHARGED PARTICLES
CONDENSED AROMATICS
CRYOGENIC FLUIDS
DATA
DATA FORMS
ELECTROMAGNETIC RADIATION
ELECTRON SPECTROSCOPY
ELECTRON SPIN RESONANCE
ELECTRONIC STRUCTURE
ELEMENTS
EXPERIMENTAL DATA
FLUIDS
GAMMA RADIATION
GRAPHS
HYDROCARBONS
INFORMATION
IONIZATION
IONIZING RADIATIONS
IONS
MAGNETIC RESONANCE
MEASURING INSTRUMENTS
NAPHTHALENE
NITROGEN
NONMETALS
NUMERICAL DATA
OPTICAL SPECTROMETERS
ORGANIC COMPOUNDS
PHENANTHRENE
PHOTOELECTRON SPECTROSCOPY
RADIATIONS
RADICALS
RESONANCE
SPECTRA
SPECTROMETERS
SPECTROSCOPY
TABLES