High-spin polyphenoxyls attached to star-shaped poly(phenyleneninylene)s

Star-shaped poly(1,2-phenylenevinylene)s 4-substituted with multiple pendant phenoxyls (2 and 3) were synthesized by polymerizing 2-bromo-4-(acetoxyphenyl)styrene in the presence of 1,3,5-triiodobenzene or 1,3,5-tris(3',5'-diiodophenyl)benzene as the core via a simple one-pot Heck reaction and subsequent hydrolysis, phenolate formation, and heterogeneous oxidation. ESR spectra indicated a delocalized spin distribution into the core parts of the star-shaped molecules. The polyradicals, 2 and 3, were in a high-spin state at low temperature, and the ferromagnetic behavior was enhanced for the polyradical with a higher molecular weight. Although an average S of 3 remained at 3/2 to 4/2, the polyradical 2 even with a spin concentration of 0.8 spin/unit revealed an average S of 7/2 to 8/2. The 1,3,5-benzene core acted as an effective magnetic coupler to align the spins of the pendant phenoxyls through the star-shaped pi-conjugated backbone.