Polymer-based emitters are a promising route to the production of low-cost, scalable solution-processable luminescent materials. Here we describe a series of acrylic oxadiazole-based donor–acceptor monomers with tunable emission from blue to orange, with quantum yields as high as 96%. By introducing structural constraints that limit donor–acceptor orbital overlap, thermally activated delayed fluorescence (TADF) was observed in these materials. Polymerization by Cu(0) reversible deactivation radical polymerization (RDRP) gave high-molecular-weight copolymers (M n > 20 kDa) with dispersities ranging from 1.10 to 1.45, using a room-temperature procedure with Cu wire as a catalyst. One of these materials, which had phenothiazine as donor moiety, exhibited conformationally dependent dual emission, giving a mixture of prompt fluorescence and delayed fluorescence peaks, whose relative ratios varied based on the amount of O2 present during measurement. We demonstrate that this material can combine prompt and delayed fluorescence to act as a single-component, all-organic, ratiometric oxygen sensor without external calibrant. Application to ratiometric oxygen sensing is demonstrated both using a polymer thin film and via incorporation of this material into water-soluble polymer dots (Pdots), with a ratiometric response to O2 throughout the range of partial pressures relevant to biological environments.
Bottlebrush copolymers provide a covalent route to multicompartment nanomaterials that remain nanosegregated regardless of environmental conditions. This is particularly advantageous when combining polymers for optoelectronics, where the ability to control the interface between multiple chemically distinct polymers can be key to a device’s function. Here we prepare bottlebrush nanofibers from an acridine- and triazine-based donor/acceptor pair, which have been shown to exhibit thermally activated delayed fluorescence (TADF) via through-space charge transfer (TSCT). By controlling the morphology of the donor and acceptor domains within the bottlebrush, random, miktoarm, and block bottlebrush morphologies are obtained. Using these materials, nanofibers may be prepared which (i) strongly exhibit TSCT TADF; (ii) exhibit switchable TSCT TADF based on aggregation of the fibers; or (iii) preserve the properties of the original donor and acceptor components. This work demonstrates that a bottlebrush strategy may be used to either force or prevent interactions between chemically dissimilar optoelectronic polymers in blended thin films. In this way, we establish a convenient method for either maximizing or minimizing donor–acceptor interactions in semiconductor polymer blends, using different arrangements of the same building blocks within a bottlebrush nanofiber.
A series of naphthalimide (NAI)-based red-emissive thermally activated delayed fluorescence (TADF) acrylic monomers has been designed and synthesized. When copolymerized with a host material by Cu(0)-reversible deactivation radical polymerization (Cu(0)-RDRP), polymers exhibiting orange to deep-red TADF were obtained with quantum yields of up to 58% in solution and 31% in the solid state. These emitters exhibit dual emission consisting of high-energy prompt fluorescence from the NAI acceptor (λ max = 340 nm in toluene) and red-delayed fluorescence from the charge-transfer process (λ max = 633−711 nm in toluene). This dual emissive property was utilized to create redto-blue temperature-responsive polymers by copolymerization of NAI−DMAC with N-isopropylacrylamide and a blue fluorescent dopant. These polymers exhibit red TADF at room temperature and blue fluorescence at 70 °C, with a high ratiometric fluorescent thermal response of 32 ± 4% K −1 . Such systems are anticipated to have utility in bioimaging, drug delivery, and temperature sensing, further expanding the range of applications for red TADF materials.
The synthesis of multicomponent nanoscale structures with precisely addressable function is critical to the discovery of both new phenomena and new applications in nanotechnology. Though self-assembly offers low-cost routes to many such materials, these methods often require building blocks with particular structural motifs, thus limiting the scope of nanomaterials that can be prepared in these ways. Herein we use a bottom-up approach based on covalent chemistry to synthesize a series of bottlebrush copolymers from red, green, and blue luminescent macromonomers, which were then used to prepare multiblock organic nanofibers structurally analogous to nanoscale RGB pixels. Efficient energy transfer from a blue fluorophore to red and green phosphors can be modulated, using the solvent polarity as a stimulus, to give aggregation-induced changes in emission color. Aggregation was also accompanied by changes in the emission lifetime of the nanofiber from the nanosecond to microsecond regime. Additionally, changes in energy transfer efficiency and interchromophore distance were quantified using a FRET model. Preliminary demonstration of these materials as polarity-sensitive inks for encryption and encoding were also demonstrated using a red/blue fluorescence switch upon exposure to solvent. Finally, the potential complexity of optoelectronic materials accessible with these methods was demonstrated by combining these building blocks with charge-transporting materials to give organic nanofibers with ordered structures mimicking that of multilayer white OLEDs. Ultimately this work describes the preparation of robust, multicomponent nanofibers from general building blocks, combining their optoelectronic properties in ways that can be both reversibly switched and temporally resolved.
Though molecules exhibiting thermally activated delayed fluorescence (TADF) have seen extensive development in organic light-emitting diodes, their incorporation into polymer nanomaterials and thin films has led to a range of applications in sensing and imaging probes. Triplet quenching can be used to probe oxygen concentration, and the reverse intersystem crossing mechanism which gives rise to TADF can also be used to measure temperature. Moreover, the long emission lifetimes of TADF materials allows for noise reduction in time-gated microscopy, making these compounds ideal for time-resolved fluorescence imaging (TRFI). A polymer matrix enables control over energy transfer between molecules, and can be used to modulate TADF behavior, solubility, biocompatibility, or desirable mechanical properties. Additionally, a polymer's oxygen permeability can be tuned to suit imaging applications in a range of media. Here we review the applications of polymer nanoparticles and films exhibiting TADF in sensing and imaging, demonstrating that this class of materials has great potential beyond electroluminescent devices still waiting to be explored.
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