Synthesis and magnetic properties of conjugated stable polyradicals

Synthesis and magnetic properties of π-conjugated stable polyradicals bearing a polyacetylene backbone are described. 2,6-Di-tert-butyl-4-ethynylphenol and 4-ethynylphenylhydrogalvinoxyl are polymerized with W, Mo chloride or Rh complex to yield their polyacetylene derivatives with molecular weight of ca. 10⁴, while 2-ethynylphenalenone gives only its oligomer. The polymers are soluble in common solvents and are converted to the corresponding conjugated polyradicals via heterogeneous chemical oxidation using PbO₂ or alkaline K₃Fe(CN)₆. The polyradicals with extremely high spin concentration (up to 4.8 × 10²³ spins/monomer mol) are obtained by regulating the oxidative conditions. The polyradicals are quite stable in solution and even in the solid state because of resonance stabilization and/or a steric effect of the substituents. Magnetic interactions between the unpaired spins in the conjugated stable polyradicals are discussed.