Suppression of Dexter transfer by covalent encapsulation for efficient matrix-free narrowband deep blue hyperfluorescent OLEDs.

Hyperfluorescence shows great promise for the next generation of commercially feasible blue organic light-emitting diodes, for which eliminating the Dexter transfer to terminal emitter triplet states is key to efficiency and stability. Current devices rely on high-gap matrices to prevent Dexter transfer, which unfortunately leads to overly complex devices from a fabrication standpoint. Here we introduce a molecular design where ultranarrowband blue emitters are covalently encapsulated by insulating alkylene straps. Organic light-emitting diodes with simple emissive layers consisting of pristine thermally activated delayed fluorescence hosts doped with encapsulated terminal emitters exhibit negligible external quantum efficiency drops compared with non-doped devices, enabling a maximum external quantum efficiency of 21.5%. To explain the high efficiency in the absence of high-gap matrices, we turn to transient absorption spectroscopy. It is directly observed that Dexter transfer from a pristine thermally activated delayed fluorescence sensitizer host can be substantially reduced by an encapsulated terminal emitter, opening the door to highly efficient 'matrix-free' blue hyperfluorescence.

Mesitylated trityl radicals, a platform for doublet emission: symmetry breaking, charge-transfer states and conjugated polymers.

Neutral π-radicals have potential for use as light emitters in optoelectronic devices due to the absence of energetically low-lying non-emissive states. Here, we report a defect-free synthetic methodology via mesityl substitution at the para-positions of tris(2,4,6-trichlorophenyl)methyl radical. These materials reveal a number of novel optoelectronic properties. Firstly, mesityl substituted radicals show strongly enhanced photoluminescence arising from symmetry breaking in the excited state. Secondly, photoexcitation of thin films of 8 wt% radical in 4,4'-bis(carbazol-9-yl)-1,1'-biphenyl host matrix produces long lived (in the order of microseconds) intermolecular charge transfer states, following hole transfer to the host, that can show unexpectedly efficient red-shifted emission. Thirdly, covalent attachment of carbazole into the mesitylated radical gives very high photoluminescence yield of 93% in 4,4'-bis(carbazol-9-yl)-1,1'-biphenyl films and light-emitting diodes with maximum external quantum efficiency of 28% at a wavelength of 689 nm. Fourthly, a main-chain copolymer of the mesitylated radical and 9,9-dioctyl-9H-fluorene shows red-shifted emission beyond 800 nm.

A Simple Molecular Design Strategy for Delayed Fluorescence toward 1000 nm.

Harnessing the near-infrared (NIR) region of the electromagnetic spectrum is exceedingly important for photovoltaics, telecommunications, and the biomedical sciences. While thermally activated delayed fluorescent (TADF) materials have attracted much interest due to their intense luminescence and narrow exchange energies (ΔEST), they are still greatly inferior to conventional fluorescent dyes in the NIR, which precludes their application. This is because securing a sufficiently strong donor-acceptor (D-A) interaction for NIR emission alongside the narrow ΔEST required for TADF is highly challenging. Here, we demonstrate that by abandoning the common polydonor model in favor of a D-A dyad structure, a sufficiently strong D-A interaction can be obtained to realize a TADF emitter capable of photoluminescence (PL) close to 1000 nm. Electroluminescence (EL) at a peak wavelength of 904 nm is also reported. This strategy is both conceptually and synthetically simple and offers a new approach to the development of future NIR TADF materials.