Abstract
Redox-induced magnetic regulation in organic diradicals is distinctly attractive. In this work, taking nitroxide radicals as spin sources, we predict the magnetic properties of 9, 10-anthraquinone, 9, 10-phenaquone, 9, 10-diazanthracene and 9, 10-diazepine-bridged molecular diradical structures in which the couplers are prone to dihydrogenation reduction at positions 9 and 10. As evidenced at both the B3LYP and M06-2X levels of theory, the calculations confirm that the magnetic transitions between ferromagnetism and antiferromagnetism can take place for 9, 10-anthraquinone and 9, 10-diazanthracene-bridged diradicals after dihydrogenation. The differences in the magnetic behaviors and magnetic magnitudes of 9, 10-anthraquinone and 9, 10-diazanthracene-bridged diradicals before and after dihydrogenation could be attributed to their noticeably different spin-interacting pathways. As for 9, 10-phenaquone and 9, 10-diazepine-bridged diradicals, the calculated results indicate that the signs of their magnetic exchange coupling constants J do not change, but the magnitudes remarkably change after dihydrogenation. The connecting bond character and spin polarization are crucial in explaining the different magnetic magnitudes of these designed diradicals. In detail, shorter bonds and larger spin polarization are responsible for strong magnetic coupling. In addition, the diradical with an extensively π-conjugated structure can effectively promote magnetic coupling. The McConnell's spin alternation rule is the key to understanding the observed ferromagnetism and antiferromagnetism of these diradicals. The work provides useful information for the rational design of redox-regulated magnetic molecular switches.