Rational design of organic diradicals with robust high-spin ground state based on antiaromatic linkers
Year: 2024
Type: article
Abstract: 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.
Source: Chemical Science
DOI: 10.1039/d4sc05225k
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: diamond
Awards: G1184413409, G145641598, G1510469474, G1864904580, G1903514128, G2262748287, G2280140124, G2819873011, G2932050808, G3005324705, G3480869486, G4181574914, G4499571919, G5555131222, G6063571778, G6122125776, G6268425849, G6731524417, G7084143925, G734693063, G7425137858, G7818408929, G782112339, G8497050386, G8684520763, G992505220
OpenAlex ID: W4404596974