Tuning the magnetic properties of a diamagnetic di-Blatter's zwitterion to antiferro- and ferromagnetically coupled diradicals.

In the quest of obtaining organic molecular magnets based on stable diradicals, we have tuned the inherent zwitterionic ground state of tetraphenylhexaazaanthracene (TPHA), a molecule containing two Blatter's moieties, by adopting two different strategies. In the first strategy, we have increased the length of the coupler between the two radical moieties and observed a transition from the zwitterionic ground state to the diradicalized state. With a larger coupler, ferromagnetic interactions are realized based on density functional theory (DFT) and wave-function theory (WFT) based complete active space self-consistent field (CASSCF)-N-electron valence state perturbation theory (NEVPT2) methods. An analysis based on the extent of spin contamination, diradical character, CASSCF orbital occupation number, Head-Gordon's index, HOMO-LUMO and SOMOs energy gaps is demonstrated that marks the transition of the ground state in these systems. In another approach, we systematically explore the effect of push-pull substitution on the way to obtain molecules based on a TPHA skeleton with diradicaloid state and, in some cases, even a triplet ground state.