Computational Design of B, N Codoped Corannulenes: Insights into Structural Stability, Bowl-Inversion Barrier, and Electronic Characteristics

Abstract

Light heteroatom-doped organic systems are attractive targets for applications in optoelectronics, catalysis, and energy devices. Herein, corannulene, a curved fragment of fullerene C60, is selected as a versatile scaffold for B and N codoping on the spoke under the constraint of no direct charge-localized B–N bonds. The resulting 33 novel isoelectronic B, N codoped systems are investigated for exploring and understanding the ground-state structural and electronic properties. All systems exhibit dynamic stability with negative formation energies relative to their constituent elemental forms, indicating their thermodynamic feasibility. Selective doping at the corannulene core significantly modulates the molecular curvature: B (N) substitution at the core increases (decreases) the bowl depth, controlling the formation energies and bowl-inversion barriers. Furthermore, B, N codoping markedly alters the corannulene electronic characteristics, such as oxidative stability, electron accepting ability, chemical reactivity, and also the excited singlet–triplet gap relative to pristine corannulene. These tunable structural and electronic properties suggest strong potential for B, N codoped corannulenes in applications such as redox and photoredox catalysis, possible host–guest interactions, multiresonance thermally activated delayed fluorescence (MR-TADF), and nonfullerene acceptors (NFA) for organic solar cells. Importantly, 6 NFA and 12 MR-TADF candidates are identified based on electron affinity, dipole oscillator strength, and excited singlet–triplet gap. The findings highlight the broad design possibilities offered by heteroatom-engineered curved π-systems and provide useful insights for the development of MR-TADF emitters and other functional organic materials for applications in energy conversion, optoelectronics, and catalysis.