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Control of the molecular configuration at the interface of an organic heterojunction is key to the development of efficient optoelectronic devices. Due to the difficulty in characterizing these buried and (probably) disordered heterointerfaces, the interfacial structure in most systems remains a mystery. Here we demonstrate a synthetic strategy to design and control model interfaces, enabling their detailed study in isolation from the bulk material. This is achieved by the synthesis of a polymer in which a non-fullerene acceptor moiety is covalently bonded to a donor polymer backbone using dual alkyl chain links, constraining the acceptor and donor units in a through space co-facial arrangement. The constrained geometry of the acceptor relative to the electron-rich and -poor moieties in the polymer backbone can be tuned to control the kinetics of charge separation and the energy of the resultant charge-transfer state giving insight into factors that govern charge generation at organic heterojunctions.

Lanthanide-doped nanoparticles (LnNPs) possess unique optical properties and are employed in various optoelectronic and bioimaging applications. One fundamental limitation of LnNPs is their low absorption cross-section. This hurdle can be overcome through surface modification with organic chromophores with large absorption cross-sections. Controlling energy transfer from organic molecules to LnNPs is crucial for creating optically bright systems, yet the mechanisms are not well understood. Using pump–probe spectroscopy, we follow singlet energy transfer (SET) and triplet energy transfer (TET) in systems comprising different length 9,10-bis(phenylethynyl)anthracene (BPEA) derivatives coordinated onto ytterbium and neodymium-doped nanoparticles. Photoexcitation of the ligands forms singlet excitons, some of which convert to triplet excitons via intersystem crossing when coordinated to the LnNPs. The triplet generation rate and yield are strongly distance-dependent. Following their generation, TET occurs from the ligands to the LnNPs, exhibiting an exponential distance dependence, independent of solvent polarity, suggesting a concerted Dexter-type process with a damping coefficient of 0.60 Å–1. Nevertheless, TET occurs with near-unity efficiency for all BPEA derivatives due to the lack of other triplet deactivation pathways and long intrinsic triplet lifetimes. Thus, we find that close coupling is primarily important to ensure efficient triplet generation rather than efficient TET. Although SET is faster, we find its efficiency to be lower and more strongly distance-dependent than the TET efficiency. Our results present the first direct distance-dependent energy transfer measurements in LnNP@organic nanohybrids and establish the advantage of using the triplet manifold to achieve the most efficient energy transfer and best sensitization of LnNPs with π-conjugated ligands.

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.

Narrow bandgap conjugated polymers are a heavily studied class of organic semiconductors, but their excited states usually have a very short lifetime, limiting their scope for applications. One approach to overcome the short lifetime is to populate long-lived triplet states for which relaxation to the ground state is forbidden. However, the triplet lifetime of narrow bandgap polymer films is typically limited to a few microseconds. Here, we investigated the effect of film morphology on triplet dynamics in red-emitting conjugated polymers based on the classic benzodithiophene monomer unit with the solubilizing alkyl side chains C16and C2C6and then used Pd porphyrin sensitization as a further strategy to change the triplet dynamics. Using transient absorption spectroscopy, we demonstrated a 0.45 ms triplet lifetime for the more crystalline nonsensitized polymer C2C6, 2–3 orders of magnitude longer than typically reported, while the amorphous C16had only a 5 μs lifetime. The increase is partly due to delaying bimolecular electron–hole recombination in the more crystalline C2C6,where a higher energy barrier for charge recombination is expected. A triplet lifetime of 0.4 ms was also achieved by covalently incorporating 5% of Pd porphyrin into the C16polymer, which introduced extra energy transfer steps between the polymer and porphyrin that delayed triplet dynamics and increased the polymer triplet yield by 7.9 times. This work demonstrates two synthetic approaches to generate the longest-lived triplet excited states in narrow bandgap conjugated polymers, which is of necessity in a wide range of fields that range from organic electronics to sensors and bioapplications.

Conjugated polymers with intense solid-state emission are vital for the development of next-generation optoelectronic devices. In particular, it remains extremely challenging to construct π-conjugated systems that emit in the red region of the electromagnetic spectrum and also retain their optical properties and intense photoluminescence in the solid state. In this article we report the synthesis and characterization of three novel diketopyrrolopyrrole-based conjugated polymers, with systematic variation of the covalent encapsulation density. Through control of the distance and density of encapsulation, our red-emitting polymers demonstrate that aggregation-caused quenching can be mostly eliminated, culminating in the most efficient solid-state photoluminescence from red conjugated polymers to date.

Intermolecular interactions play a fundamental role on the performance of conjugated materials in organic electronic devices, as they heavily influence their optoelectronic properties. Synthetic control over the solid state properties of organic optoelectronic materials is crucial to access real life applications. Perylene diimides (PDIs) are one of the most highly studied classes of organic fluorescent dyes. In the solid state, π–π stacking suppresses their emission, limiting their use in a variety of applications. Here, we report the synthesis of a novel PDI dye that is encapsulated by four alkylene straps. X-ray crystallography indicates that intermolecular π–π stacking is completely suppressed in the crystalline state. This is further validated by the photophysical properties of the dye in both solution and solid state and supported by theoretical calculations. However, we find that the introduction of the encapsulating “arms” results in the creation of charge-transfer states which modify the excited state properties. This article demonstrates that molecular encapsulation can be used as a powerful tool to tune intermolecular interactions and thereby gain an extra level of control over the solid state properties of organic optoelectronic materials.

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 ΔESTrequired 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.

We report the synthesis and structural and photophysical characterization of two series of molecules with functionalized azatriangulene electron donor cores and three pendant electron acceptor units. The presented donor and acceptor units are joined by C–C bonds, instead of the usual C–heteroatom bonds often found in thermally activated delayed fluorescence (TADF) emitters. The effects of the donor–acceptor strength and donor–acceptor dihedral angle on the emission properties are assessed. The data establish that the singlet–triplet energy gap is >0.3 eV and that delayed emission is present in only specific host matrices, irrespective of host polarity. Specific host behavior is atypical of many TADF materials, and we suggest the delayed emission in this work does not occur by a conventional vibronically coupled TADF mechanism, as the ΔESTvalue is too large. Detailed photophysical analysis and supporting density functional theory calculations suggest that some presented azatriangulene molecules emit via an upper-triplet state crossing mechanism. This work highlights that several different mechanisms can be responsible for delayed emission, often with highly similar photophysics. Detailed photophysical analysis is required to establish which delayed emission mechanism is occurring. Our results also highlight a clear future direction toward vibronically coupled C–C bonded TADF materials.

The application of a chiral auxiliary ligand to control the diastereoselectivity in the synthesis of a cyclometalated iridium(III) complex is presented. The diastereomeric iridium(III) complexes 1aand 1bare reported, in which a phenoxyoxazoline auxiliary ligand incorporates a chiral center functionalized with a pendant pentafluorophenyl group. The diastereomers were readily separated, and their structural, electrochemical and photophysical properties are discussed. Solution-state NMR data and X-ray crystal structures establish that the pentafluorophenyl group engages in intramolecular π–π interactions. The X-ray analysis reveals that the two diastereomers display very different modes of intramolecular stacking. The variable-temperature 19F NMR data indicate that rotation of the pendant pentafluorophenyl rings in 1band 1ais a temperature-dependent process and that there is a smaller energy barrier to rotation in 1bin comparison to 1a. This correlates with variable-temperature photoluminescence data, which show that upon heating the integrated emission intensity is reduced substantially more for 1bthan for 1a, which is ascribed to the enhanced rotation in 1b, providing a more easily populated nonradiative pathway in comparison to 1a. These experimental data are supported by computational calculations. Phosphorescent organic light-emitting devices (PhOLEDs) using 1aas the dopant complex give blue-green emission with a high maximum external quantum efficiency (EQEmax) of 25.8% (at ca. 270 cd m–2) and with a low efficiency roll-off to 24.9% at 1000 cd m–2. Our results extend the scope of ligand design for cyclometalated iridium complexes which possess interesting structural and emission properties.

Intramolecular singlet fission (iSF) facilitates single-molecule exciton multiplication, converting an excited singlet state to a pair of triplet states within a single molecule. A critical parameter in determining the feasibility of SF-enhanced photovoltaic designs is the triplet energy; many existing iSF materials have triplet energies too low for efficient transfer to silicon via a photon multiplier scheme. In this work, a series of six novel dimers based upon the high-triplet-energy, SF-active chromophore, 1,6-diphenyl-1,3,5-hexatriene (DPH) [E(T1) ∼ 1.5 eV], were designed, synthesized, and characterized. Transient absorption spectroscopy and fluorescence lifetime studies reveal that five of the dimers display iSF activity, with time constants for singlet fission varying between 7 ± 2 ps and 2.2 ± 0.2 ns and a high triplet yield of 163 ± 63% in the best-performing dimer. A strong dependence of the rate of fission on the coupling geometry is demonstrated. For optimized iSF behavior, close spatial proximity and minimal through-bond communication are found to be crucial for balancing the rate of SF against the reverse recombination process.