Highly Efficient Tuning of Ferromagnetic Spin Interactions in High-Spin Arylamine Structures by Incorporation of Spin Bearing Carbazole Units

Arylamine moieties oxidized to radical cations are considered promising spin bearing units in high-spin-type compounds. Here, we report the first use of carbazole-3,6-diamine units as efficient, rigid spin containing units. The use of rigid spin bearing units enhances significantly spin exchange interactions. The design using density functional theory calculations shows the progressive increase of the exchange coupling constant dependent on the considered model molecules. Two of the most representative molecules containing flexible (dimer 1) and rigid spin coupling unit (dimer 2) were synthesized. Electrochemical and pulsed-electron paramagnetic resonance nutation studies showed that both dimers can be oxidized to yield a majority of dicationic diradicals exhibiting S = 1 ground states. The high values of the dimer 2 exchange coupling constant obtained both computationally (J/kB = 145 K; HHeis. = −JS1S2) and experimentally (J/kB = 90–100 K) indicate the beneficial role of the carbazole moiety incorporated...