Garner, Marc H.Blaskovits, J. TerenceCorminboeuf, Clemence2024-02-232024-02-232024-02-232024-01-1510.1039/d3cc05747jhttps://infoscience.epfl.ch/handle/20.500.14299/205433WOS:001153492200001Inverted singlet-triplet gaps may lead to novel molecular emitters if a rational design approach can be achieved. We uncover a substituent strategy that enables tuning of the gap and succeed in inducing inversion in near-gapless molecules. Based on known inverted-gap emitters, we design substituted analogs with even more negative singlet-triplet gaps than in the parent systems. The inversion is lost if the reverse substituent-strategy is used. We thus demonstrate a definite set of conceptual design rules for inverted gap molecules.|A substituent-based design strategy induces and enhances inversions in the excited state singlet-triplet gaps in a wide range of potential organic light-emitting molecules.Physical SciencesElectronically Excited-StatesDelayed FluorescenceMultiplicity RuleViolationMoleculesPairstext::journal::journal article::research article