Reaching optimal light-induced intramolecular spin alignment within photomagnetic molecular device prototypes.

Ground-state (GS) and excited-state (ES) properties of novel photomagnetic molecular devices (PMMDs) are investigated by means of density functional theory. These organic PMMDs undergo a ferromagnetic alignment of their intramolecular spins in the lowest ES. They are comprised of: 1) an anthracene unit (An) as both the photosensitizer (P) and a transient spin carrier (SC) in the triplet ES ((3)An*); 2) imino-nitroxyl (IN) or oxoverdazyl (OV) stable radical(s) as the dangling SC(s); and 3) bridge(s) (B) connecting peripheral SC(s) to the An core at positions 9 and 10. Improving the efficiency of the PMMDs involves strengthening the ES intramolecular exchange coupling (J(ES)) between transient and persistent SCs, hence the choice of 2-pyrimidinyl (pm) as B elements to replace the original p-phenylene (ph). Dissymmetry of the pm connectors leads to [SC-B-P-B-SC] regio-isomers int. and ext., depending on whether the pyrimidinic nitrogen atoms point towards the An core or the peripheral SCs, respectively. For the int. regio-isomers we show that the photoinduced spin alignment is significantly improved because the J(ES)/k(B) value is increased by a factor of more than two compared with the ph-based analogue (J(ES)/k(B)>+400 K). Most importantly, we show that the optimal J(ES)/k(B) value ( approximately +600 K) could be reached in the event of an unexpected saddle-shaped structural distortion of the lowest ES. Accounting for this intriguing behavior requires dissection of the combined effects of 1) borderline intramolecular steric hindrance about key An-pm linkages, which translates into the flatness of the potential energy surface; 2) spin density disruption due to the presence of radicals; and 3) possibly intervening photochemistry, with An acting as a light-triggered electron donor while pm, IN, and OV behave as electron acceptors. Finally, potentialities attached to the (SC)-pm-An-pm pattern are disclosed.