Exchange Interaction in Covalently Bonded Biradical−Monoradical Composite Molecules

As a novel molecular designing for genuinely organic molecule-based ferrimagnets, we have proposed a
strategy of “single-component ferrimagnetics”. When a π-biradical with an S = 1 ground state and a
π-monoradical with S = 1/2 are united by σ-bonds, the π-conjugation between the biradical and the monoradical
moieties should be truncated in the resultant triradical. This gives magnetic degrees of freedom for both S =
1 and 1/2 in the single molecule, serving as a building block for organic molecule-based ferrimagnets under
favorable conditions (single-component ferrimagnetics). We have designed and synthesized a triradical, 3-(1‘-oxyl-3‘-oxido-4‘,4‘,5‘,5‘-tetramethylimidazolin-2-yl)benzoic acid 2,4-bis(1‘ ‘-oxyl-3‘ ‘-oxido-4‘ ‘,4‘ ‘,5‘ ‘,5‘ ‘-tetramethylimidazolin-2-yl)phenyl ester (4), as a model compound for the novel approach to genuinely organic
ferrimagnets. In the triradical 4, a m-phenylene-bis(nitronyl nitroxide) biradical with a triplet (S = 1) ground
state is united with a phenyl nitronyl nitroxide monoradical (S = 1/2) by an ester coupler. Solution-phase ESR
spectra from 4 exhibited a complex hyperfine splitting due to 14N and 1H nuclei. The analysis of the hyperfine
structure based on perturbation calculations has revealed that the exchange interaction within the biradical
moiety is much larger than those between the biradical and the monoradical moieties and the magnetic degrees
of freedom for both S = 1 and 1/2 are retained in 4. An X-ray crystal structure analysis showed that the
triradical molecules are arranged in a one-dimensional molecular chain in the crystal. The magnetic susceptibility
in a crystalline solid state is consistent with the crystal structure.