Coulombic control of charge transfer in radicals with quartet recycling luminescence

Excitons in organic materials are emerging as an attractive platform for tunable quantum technologies. Structures with near-degenerate doublet and triplet excitations in linked trityl radical, acene and carbazole units can host quartet states. These high spin states can be coherently manipulated, and later decay radiatively via the radical doublet transition. However, this requires controlling the deexcitation pathways of all metastable states. Here we establish design rules for efficient quartet generation and recycling to luminescence, using different connection arrangements of the molecular units. We discover that electronic coupling strength between these units dictates quartet formation and delayed emission yields, particularly through a Coulombically tuned acene-radical charge transfer state. This state acts as a source of non-radiative decay when acene-radical separation is small, but facilitates reversible doublet-quartet interconversion when acene-radical separation is large. Using these rules we report a material with 55% luminescence yield, where 94% of emitting excitons are recycled from the quartet with a 1.0 μs lifetime. This reveals the central role of molecular topology in luminescent quantum materials.