Fluorescence imaging in living cells is key to understanding many biological processes, yet autofluorescence from the sample can lower sensitivity and hinder high-resolution imaging. Time-gated measurements using phosphorescent metal complexes can improve imaging, at the cost of potential toxicity from the use of heavy metals. Here, we describe orange/red-emitting polymer dots (Pdots) exhibiting thermally activated delayed fluorescence (TADF) for time-gated imaging. Inspired by the cell invasion mechanism of the HIV TAT protein, the Pdots were formed from block copolymers composed of a hydrophilic guanidine-rich block as a cell-penetrating peptide mimic, and a rigid organic semiconductor block to provide efficient delayed fluorescence. These all-organic polymer nanoparticles were shown to efficiently enter HeLa, CHO, and HepG2 cells within 30 min, with cell viabilities remaining high for Pdot concentrations up to 25 mg mL–1. Pdot quantum yields were as high as 0.17 in aerated water, with the Pdot structure effectively shielding the TADF emitters from quenching by oxygen. Colocalization experiments revealed that the Pdots primarily accumulate outside of lysosomes, minimizing lysosomal degradation. When used for fixed cellular imaging, Pdot-incubated cells showed high signal-to-background ratios compared to control samples with no Pdot exposure. Using time-resolved spectroscopy, the delayed emission of the TADF materials was effectively separated from that of both a biological serum and a secondary fluorescent dye.

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.

A series of acrylic monomers exhibiting bright and tunable thermally activated delayed fluorescence was synthesized based on a D−π–A design with a pyrimidine acceptor and heterocyclic amine donors. Cu(0) reversible deactivation radical polymerization of these monomers in a phenylcarbazole-based host yielded random copolymers with emission quantum yields up to 0.98 in thin films and short delayed fluorescence lifetimes as low as 2.5 μs. In all cases, monomer conversions of >95% were achieved with dispersities as low as 1.14. Kinetic studies of the polymerizations revealed differences in the rates at which host and emitter monomers react, leading to either homogeneous or gradient random copolymers, depending on the nature of the electronic donor moiety. The results indicate a complex interplay between the electronic influence of the donors on the photophysical properties and their steric involvement in polymerization, which may influence their performance in optoelectronic devices.

Fluorescence imaging of living cells is key to better understanding cellular morphology and biological processes.

Thermally activated delayed fluorescence (TADF) sensitization of fluorescence is a promising strategy to improve the color purity and operational lifetime of conventional TADF organic light-emitting diodes (OLEDs). Here, we propose a new design strategy for TADF-sensitized fluorescence based on acrylic polymers with a pendant energy-harvesting host, a TADF sensitizer, and fluorescent emitter monomers. Fluorescent emitters were rationally designed from a series of homologous polycyclic aromatic amines, resulting in efficient and color-pure polymeric fluorophores capable of harvesting both singlet and triplet excitons. Macromolecular analogues of blue, green, and yellow fourth-generation OLED emissive layers were prepared in a facile manner by Cu(0) reversible deactivation radical polymerization, with emission quantum yields up to 0.83 in air and narrow emission bands with full width at half-maximum as low as 57 nm. White-light emission can easily be achieved by enforcing incomplete energy transfer between a deep blue TADF sensitizer and yellow fluorophore to yield a single white-emissive polymer with CIE coordinates (0.33, 0.39) and quantum yield 0.77. Energy transfer to the fluorescent emitters occurs at rates of 1–4 × 108 s–1, significantly faster than deactivation caused by internal conversion or intersystem crossing. Rapid energy transfer facilitates high triplet exciton utilization and efficient sensitized emission, even when TADF emitters with a low quantum yield are used as photosensitizers. Our results indicate that a broad library of untapped polymers exhibiting efficient TADF-sensitized fluorescence should be readily accessible from known TADF materials, including many monomers previously thought unsuitable for use in OLEDs.