Tuning of ferromagnetic spin interactions in polymeric aromatic amines via modification of their π-conjugated system.

Polyarylamine containing meta-para-para-aniline units in the main chain and meta-para-aniline units in the pendant chains was synthesized. The polymer can be oxidized to radical cations in chemical or electrochemical ways. The presence of meta-phenylenes in the polymer chemical structure allows for the ferromagnetic coupling of electronic spins, which leads to the formation of high spin states. Detailed pulsed-EPR study indicates that the S = 2 spin state was reached for the best oxidation level. Quantitative magnetization measurements reveal that the doped polymer contains mainly S = 2 spin states and a fraction of S = 3/2 spin states. The efficiency of the oxidation was determined to be 74%. To the best of our knowledge, this polymer is the first example of a linear doped polyarylamine combining such high spin states with high doping efficiency.