Triplet-Fusion Upconversion Using a Rigid Tetracene Homodimer.

We demonstrate that a structurally rigid, weakly coupled molecular dimer can replace traditional monomeric annihilators for triplet fusion upconversion (TUC) in solution by observing emitted photons (λ = 540 nm) from a norbornyl-bridged tetracene homodimer following excitation of a triplet sensitizer at λ = 730 nm. Intriguingly, steady-state spectroscopy, kinetic simulations, and Stern-Volmer quenching experiments show that the dimer exhibits qualitatively different photophysics than its parent monomer: it is less effective at diffusion-mediated triplet exciton transfer, but it fuses extracted triplets more efficiently. Our results support the development of composite triplet-fusion platforms that go beyond diffusion-mediated triplet extraction, ultimately circumventing the concentration dependence of solution-phase TUC.