Antiaromatic Molecules as Magnetic Couplers: A Computational Quest.

In this study, we investigate a set of organic diradical structures in which two oxo-verdazyl radicals are selected as radical spin centers that are connected (coupled) via six coupler molecules (CM), resulting in various magnetic (ferromagnetic (FM) or antiferromagnetic (AFM)) characteristics, as reflected by their exchange coupling constants ( J ). We have designed 12 diradicals with 6-antiaromatic couplers coupled with bis-oxo-verdazyl diradicals with meta-meta (m-m) and para-meta (p-m) positional connectivities. The nature of the magnetic coupling (ferromagnetic, nonmagnetic, or antiferromagnetic) and the magnitude of the exchange constant J depend on the type of coupler, the connecting point between each radical center and CM, the degree of aromaticity of the coupler, and the length of the through-bond distance between radical centers. The computed magnetic exchange coupling constants J for these diradicals at the B3LYP/6-311++G(d,p) and MN12SX/6-311++G(d,p) levels of theory are large for many of these structures, indicating strong ferromagnetic coupling (with positive J values). In some cases, magnetic couplings are observed with J > 1000 cm -1 (B3LYP/6-311++G(d,p)) and strong antiferromagnetic coupling (with negative J values) with J < -1000 cm -1 (B3LYP/6-311++G(d,p)). Similarly, in some cases, magnetic couplings are observed with J > 289 cm -1 (MN12SX/6-311++G(d,p)) and strong antiferromagnetic coupling (with negative J values) with J < -568 cm -1 (MN12SX/6-311++G(d,p)). Furthermore, while numerous studies have reported that the degree of aromaticity of molecular couplers often favors strong ferromagnetic coupling, displaying the high-spin character of diradicals in their ground states, the couplers chosen in this study are characterized as antiaromatic or nonaromatic. The current investigation provides evidence that, remarkably, antiaromatic couplers are able to enhance stability by favoring electronic diradical structures with very strong ferromagnetic coupling when the length of the through-bond distance and connectivity pattern between radical centers are selected in such a way that the FM coupling is optimized. The findings in this study offer new strategies in the design of novel organic materials with interesting magnetic properties for practical applications.