Magnetic coupling modulation in meta -nitroxide-functionalized isoalloxazine magnets with redox-active units as efficient side-modulators

Magnetic conversion can be accomplished in a variety of ways, as organic molecules with switchable magnetic characteristics offer numerous technological applications. It is crucial to find magnetism-switchable systems because, in the field of organic magnetic materials, the redox-induced magnetic reversal is very simple to achieve and shows significant applications. Herein, we computationally design isoalloxazine-based diradicals through oxidizing N10 and adding a nitroxide to C8 as the spin source ( 8-nitroxide-isoalloxazine 10-oxide, an -phenylene-like nitroxide diradical expanded with a redox unit as a side-modulator) and its N1/N5-hydrogenated/protonated diradical derivatives and introducing substituents (-OH, -NH , and -NO ) to C6. We demonstrate that the basically modified structure exhibits ferromagnetic (FM) characteristics with a magnetic coupling constant ( ) of 561.3 cm calculated at the B3LYP/6-311+G(d,p) level, obeying the -phenylene-mediated diradical character, and dihydrogenation can lead to an AFM diradical with considerably large (-976.1 cm ). Surprisingly, protonation at N1 or N5 can lead to distinctly different magnetic variations (561.3 → -1602.9 cm at N1 561.3 → 379.1 cm at N5). Analyses indicate that small singlet-triplet energy gaps and small energy gaps between the highest occupied and lowest unoccupied molecular orbitals (HOMO, LUMO) of the closed shell singlet state are the key features of these isoalloxazine diradicals, and aromaticity variations, significant spin delocalization from the π-conjugated structure and spin polarization from the non-Kekule structure induced by modification are responsible for the magnetic conversion. Furthermore, the spin alternation rule, the singly occupied molecular orbital (SOMO) effect, and the SOMO-SOMO energy splitting of the triplet state are used to analyze these distinct variations. This work provides a novel understanding of the structures and characteristics of modified isoalloxazine diradicals, as well as essential details for the intricate design and characterization of new isoalloxazine-based potential organic magnetic switches.