Summary
Single crystals of malonic acid (CH2(COOH)2), have been irradiated with 4.0MeV electrons at liquid nitrogen temperature. The induced radicals have been identified by electron spin resonance technique. ESR lines due to different conformations of the ĊH2(COOH) radical are observed. ESR lines due to the ĊOOH radical are also seen. It is suggested that the fragmentation into these radicals takes place preferentially on one side of the molecule and subsequent to the ionization event. Upon warming of the crystal to room temperature, the ĊOOH radical disappears and the ĊH(COOH)2 radical is formed. The latter radical seems to exist in two slightly different modifications.
Similar content being viewed by others
References
Beveridge, D. L., McIver, J. W., Jr.: INDO molecular orbital study of hyperfine tensors: theory, methodology, and applications to CH, CH3, and radicaloid derivatives of malonic acid. J. chem. Phys.54, 4681–4690 (1971).
Ghosh, D. K., Whiffen, D. H.: The electron spin resonance spectrum ofγ-irradiated single crystal of glycine. Molec. Phys.2, 285–300 (1959).
Goedkoop, J. A. and Mac Gillavry, C. H.: The crystal structure of malonic acid. Acta Cryst.10, 125–127 (1957).
Heller, H. C., McConnell, H. M.: Radiation Damage in organic crystals. II: (C02H) CH (CO2H) inβ-succinic acid. J. chem. Phys.32, 1535–1539 (1960).
Holden, A. N., Kettel, C., Merritt, F. R., Yager, W. A.: Determination ofg-values in paramagnetic organic compounds by microwave resonance. Physiol. Rev.77, 147–148 (1950).
Horsfield, A., Morton, J. R., Whiffen, D. H.: Electron spin resonance ofγ-irradiated malonic acid. Molec. Phys.4, 327–332 (1961).
McConnell, H. M., Strathdee, T.: Theory of anisotropic hyperfine interactions inπ-electron radicals. Molec. Phys.2, 129–138 (1959).
McConnell, H. M., Heller, C., Cole, T., Fessenden, R. W.: Radiation damage in organic crystals. I: CH(COOH)2 in malonic acid. J. Amer. chem. Soc.82, 766–775 (1960).
Morton, J. R.: Electron spin resonance spectra of oriented radicals. Chem. Rev.64, 453–471 (1964).
Schonland, D. S.: On the determination of the principalg-values in electron spin resonance. Proc. physiol. Soc.73, 788–792 (1959).
Stone, E. W., Maki, A. H.: Hindered internal rotation and ESR spectroscopy. J. chem. Phys.37, 1326–1333 (1962).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Bergene, R., Melø, T.B. Free radicals in malonic acid: A study of radical conformations at 77 K and 295 K by the ESR-technique. Biophysik 9, 1–12 (1972). https://doi.org/10.1007/BF01293477
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF01293477