Imidazophenothiazine-Based Thermally Activated Delayed Fluorescence Materials with Ultra-Long-Lived Excited States for Energy Transfer Photocatalysis.

Triplet-triplet energy transfer (EnT) is a powerful activation pathway in photocatalysis that unlocks new organic transformations and improves the sustainability of organic synthesis. Many current examples, however, still rely on platinum-group metal complexes as photosensitizers, with associated high costs and environmental impacts. Photosensitizers that exhibit thermally activated delayed fluorescence (TADF) are attractive fully organic alternatives in EnT photocatalysis. However, TADF photocatalysts incorporating heavy atoms remain rare, despite their utility in inducing efficient spin-orbit-coupling, intersystem-crossing, and consequently a high triplet population. Here, we describe the synthesis of imidazo-phenothiazine (IPTZ), a sulfur-containing heterocycle with a locked planar structure and a shallow LUMO level. This acceptor is used to prepare seven TADF-active photocatalysts with triplet energies up to 63.9 kcal mol-1. We show that sulfur incorporation improves spin-orbit coupling and increases triplet lifetimes up to 3.64 ms, while also allowing for tuning of photophysical properties via oxidation at the sulfur atom. These IPTZ materials are applied as photocatalysts in five seminal EnT reactions: [2 + 2] cycloaddition, the disulfide-ene reaction, and Ni-mediated C-O and C-N cross-coupling to afford etherification, esterification, and amination products, outcompeting the industry-standard TADF photocatalyst 2CzPN in four of the five studied scenarios. Detailed photophysical and theoretical studies are used to understand structure-activity relationships and to demonstrate the key role of the heavy atom effect in the design of TADF materials with superior photocatalytic performance.

Dibenzodipyridophenazines with Dendritic Electron Donors Exhibiting Deep-Red Emission and Thermally Activated Delayed Fluorescence.

The development of deep-red thermally activated delayed fluorescence (TADF) emitters is important for applications such as organic light-emitting diodes (OLEDs) and biological imaging. Design strategies for red-shifting emission include synthesizing rigid acceptor cores to limit nonradiative decay and employing strong electron-donating groups. In this work, three novel luminescent donor-acceptor compounds based on the dibenzo[a,c]dipyrido[3,2-h:20-30-j]-phenazine-12-yl (BPPZ) acceptor were prepared using dendritic carbazole-based donors 3,3″,6,6″-tetramethoxy-9'H-9,3':6',9″-tercarbazole (TMTC), N3,N3,N6,N6-tetra-p-tolyl-9H-carbazole-3,6-diamine (TTAC), and N3,N3,N6,N6-tetrakis(4-methoxyphenyl)-9H-carbazole-3,6-diamine (TMAC). Here, dimethoxycarbazole, ditolylamine, and bis(4-methoxyphenyl)amine were introduced at the 3,6-positions of carbazole to increase the strength of these donors and induce long-wavelength emission. Substituent effects were investigated with experiments and theoretical calculations. The emission maxima of these materials in toluene were found to be 562, 658, and 680 nm for BPPZ-2TMTC, BPPZ-2TTAC, and BPPZ-2TMAC, respectively, highlighting the exceptional strength of the TMAC donor, which pushes the emission into the deep-red region of the visible spectrum as well as into the biological transparency window (650-1350 nm). Long-lived emission lifetimes were observed in each emitter due to TADF in BPPZ-2TMC and BPPZ-2TTAC, as well as room-temperature phosphorescence in BPPZ-2TMAC. Overall, this work showcases deep-red emissive dendritic donor-acceptor materials which have potential as bioimaging agents with emission in the biological transparency window.

Polymer dots and glassy organic dots using dibenzodipyridophenazine dyes as water-dispersible TADF probes for cellular imaging.

Fluorescence imaging of living cells is key to better understanding cellular morphology and biological processes. Water-dispersible nanoparticles exhibiting thermally activated delayed fluorescence (TADF) have recently emerged as useful probes for time-resolved fluorescence imaging (TRFI), circumventing interference from biological autofluorescence. Many existing approaches, however, require TADF dyes with specific structural features, precluding many high-performance TADF materials from being used in this application. Here, we describe the synthesis of two TADF emitters based on the rigid and strongly electron-withdrawing dibenzo[a,c]dipyrido[3,2-h:2'-3'-j]phenazine-12-yl (BPPZ) motif, and demonstrate two parallel approaches for the encapsulation of these fluorophores to yield water-dispersible nanoparticles suitable for TRFI. First, fluorescent polymer dots (Pdots) were formed by dye encapsulation within cell-penetrating amphiphilic copolymers. Glassy organic nanoparticles (g-Odots) were also prepared, giving nanoparticles with higher photoluminescence quantum yields and improved colour purity. Both approaches yielded nanoparticles suitable for imaging, with reasonable uptake and cytotoxicity on the timescale of standard imaging experiments using human cervical (HeLa) and liver (HepG2) cancer cell lines. This work demonstrates two flexible strategies for preparing water-dispersible TADF nanoparticles for TRFI, both of which should be readily adaptable to nearly any existing hydrophobic TADF dye.

An imidazoacridine-based TADF material as an effective organic photosensitizer for visible-light-promoted [2 + 2] cycloaddition.

Energy transfer (EnT) is a fundamental activation process in visible-light-promoted photocycloaddition reactions. This work describes the performance of imidazoacridine-based TADF materials for visible-light mediated triplet-triplet EnT photocatalysis. The TADF material ACR-IMAC has been discovered as an inexpensive, high-performance organic alternative to the commonly used metal-based photosensitizers for visible-light EnT photocatalysis. The efficiency of ACR-IMAC as a photosensitizer is comparable with Ir-based photosensitizers in both intra- and intermolecular [2 + 2] cycloadditions. ACR-IMAC mediated both dearomative and non-dearomative [2 + 2] cycloadditions in good yields, with high regio- and diastereocontrol. Cyclobutane-containing bi- tri- and tetracylic scaffolds were successfully prepared, with broad tolerance toward functional groups relevant to drug discovery campaigns. Fluorescence quenching experiments, time-correlated single-photon counting, and transient absorption spectroscopy were also conducted to provide insight into the reaction and evidence for an EnT mechanism.

Polymer Dots with Enhanced Photostability, Quantum Yield, and Two-Photon Cross-Section using Structurally Constrained Deep-Blue Fluorophores.

Semiconducting polymer dots (Pdots) have emerged as versatile probes for bioanalysis and imaging at the single-particle level. Despite their utility in multiplexed analysis, deep blue Pdots remain rare due to their need for high-energy excitation and sensitivity to photobleaching. Here, we describe the design of deep blue fluorophores using structural constraints to improve resistance to photobleaching, two-photon absorption cross sections, and fluorescence quantum yields using the hexamethylazatriangulene motif. Scanning tunneling microscopy was used to characterize the electronic structure of these chromophores on the atomic scale as well as their intrinsic stability. The most promising fluorophore was functionalized with a polymerizable acrylate handle and used to give deep-blue fluorescent acrylic polymers with Mn > 18 kDa and D < 1.2. Nanoprecipitation with amphiphilic polystyrene-graft-(carboxylate-terminated poly(ethylene glycol)) gave water-soluble Pdots with blue fluorescence, quantum yields of 0.81, and molar absorption coefficients of (4 ± 2) × 108 M-1 cm-1. This high brightness facilitated single-particle visualization with dramatically improved signal-to-noise ratio and photobleaching resistance versus an unencapsulated dye. The Pdots were then conjugated with antibodies for immunolabeling of SK-BR3 human breast cancer cells, which were imaged using deep blue fluorescence in both one- and two-photon excitation modes.

Thermally Activated Delayed Fluorescence in 1,3,4-Oxadiazoles with π-Extended Donors.

Here, we describe the synthesis of five 1,3,4-oxadiazole-based donor-acceptor materials, using dendritic carbazole-based donors 9'H-9,3':6'9″-tercarbazole (terCBz) and N3,N3,N6,N6-tetra-p-tolyl-9H-carbazole-3,6-diamine (TTAC). Due to the strongly donating and highly twisted nature of the TTAC donor as well as the spatially separated hole-particle wavefunctions, three of the five compounds exhibited thermally activated delayed fluorescence (TADF) in spite of a relatively large ΔEST measured through phosphorimetry (0.33-0.37 eV). These materials demonstrated photoluminescence quantum yields as high as 0.89 in toluene, with emission maxima ranging from 474 to 495 nm in the solid state. Additionally, two materials containing only terCBZ donor(s) exhibited deep blue fluorescence, with Commission Internationale de l'éclairage coordinates of (0.16, 0.05); the weaker nature of the terCBz donor results in a prohibitively large ΔEST (0.68-0.77 eV). A gap-tuned range-separated hybrid functional (ωB97XD*) was used to rigorously calculate triplet energies, while a systematic analysis of electronic structures and photophysical properties provided further insight into the properties of these materials. These findings ultimately contribute a synthetically facile approach toward highly emissive TADF emitters using a 1,3,4-oxadiazole motif.

1,8-Naphthalimide-Based Polymers Exhibiting Deep-Red Thermally Activated Delayed Fluorescence and Their Application in Ratiometric Temperature Sensing.

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 (λmax = 340 nm in toluene) and red-delayed fluorescence from the charge-transfer process (λmax = 633-711 nm in toluene). This dual emissive property was utilized to create red-to-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.

Enhanced Glutathione Peroxidase Activity of Water-Soluble and Polyethylene Glycol-Supported Selenides, Related Spirodioxyselenuranes, and Pincer Selenuranes.

Diaryl selenides containing o-hydroxymethylene substituents function as peroxide-destroying mimetics of the antioxidant selenoenzyme glutathione peroxidase (GPx), via oxidation to the corresponding spirodioxyselenuranes with hydrogen peroxide and subsequent reduction back to the original selenides with glutathione. Parent selenides with 3-hydroxypropyl or 2,3-dihydroxypropyl groups produced the novel compounds 10 and 11, respectively, with greatly improved aqueous solubility and catalytic activity. The phenolic derivative 28 displayed similarly ameliorated properties and also modest radical-inhibiting antioxidant activity, as evidenced by an assay based on phenolic hydrogen atom transfer to the stable free radical DPPH. In contrast, several selenides that afford pincer selenuranes (e.g., 20 and 21) instead of spiroselenuranes upon oxidation showed inferior catalytic activity. Several selenide analogues were attached to polyethylene glycol (PEG) oligomers, as PEG substituents can improve water solubility and bioavailability, while retarding clearance. Again, the PEG derivatives afforded remarkable activity when oxidation generated spirodioxyselenuranes and diminished activity when pincer compounds were produced. Several such compounds proved to be ca. 10- to 100-fold catalytically superior to the diaryl selenides and their spirodioxyselenurane counterparts investigated previously. Finally, an NMR-based assay employing glutathione in D2O was designed to accommodate the faster reacting water-soluble mimetics and to more closely duplicate in vivo conditions.