Fully-organic molecules with high-spin ground states are promising building blocks for new lightweight flexible magnetic materials for emerging technological applications (e.g. spintronics). In this study, we explore the potential of diradicals made of two diphenylmethyl-based open-shell cores covalently linked via different types of pentalene and diazapentalene-based antiaromatic couplers (including dibenzopentalenes and acene-inserted derivatives). Accurate electronic structure calculations have been employed to target non-bonding and non-disjoint frontier molecular orbitals that favor high-spin configurations, leading to the identification of diradicals displaying robust triplet ground states. These candidates exhibit singlet-triplet energy gaps that are up to ten times the thermal energy at room temperature. These substantial gaps emerge from strong interactions between the π-systems of the open-shell centers and the antiaromatic coupler. These interactions not only result in high spin states but are also found to lead to an enhanced stability of the diradicals by drastically dampening their inherent antiaromatic character as compared to the bare couplers, and promoting a high degree of spin density delocalization. These findings highlight the potential of pentalene-based diradicals as building blocks for developing new advanced fully organic magnetic materials.
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