Paramagnetic Resonance Absorption in Some Organic Biradicals

Abstract

Four compounds of the form 4,4′‐polymethylenebistriphenylmethyl, one compound of the form (1,4‐phenylene)bisdiarylmethyl, three compounds of the form (4,4′‐biphenylene)bisdiarylmethyl, and one compound, 4,4′‐oxybistriphenylmethyl have been shown to possess unpaired electrons by paramagnetic resonance absorption. The resonance spectra of 0.01 M solutions of these compounds in benzene exhibit a hyperfine structure arising from a spherically symmetrical contribution of the magnetic dipole interaction between the unpaired electron and the nuclear magnetic moments of the hydrogen atoms. The g‐factors for the compounds investigated in the first three classes were found to be 2.0025±0.0004 and 2.0031±0.0004 for the last compound. Such a close approach of the g‐factor to the free electron value plus the sharpness of the hyperfine structure lines indicates that the anisotropic contributions of the spin‐orbit interaction, which would normally lift the degeneracy of the triplet state, are averaged out by the tumbling of the molecules.