Design,synthesis, and properties of polystyrene-based through-space charge transfer polymers: Effect of triplet energy level of electron donor moiety on delayed fluorescence and electroluminescence performance

Two kinds of polystyrene-based through-space charge transfer (TSCT) polymers consisting of spatially-separated acridan donor moieties bearing phenyl or naphthyl substituents and triazine acceptor moieties are designed and synthesized. It is found that TSCT polymers containing phenyl-substituted acridan donors exhibit high-lying singlet (S₁) and triplet (T₁) states with small singlet-triplet energy splitting (∆E_ST) of 0.04–0.05 eV, resulting in thermally activated delayed fluorescence (TADF) with reverse intersystem crossing rate constants of 1.1–1.2 × 10⁶ s⁻¹. In contrast, polymers bearing naphthyl-substituted acridan donors, although still having TSCT emission, exhibit no TADF effect because of the large ∆E_ST of 0.30–0.33 eV induced by low-lying locally excited T₁ state of naphthyl donor moiety. Solution-processed organic light-emitting diodes using TSCT polymers containing phenyl-substituted acridan donors reveal sky-blue emission at 483 nm together with maximum external quantum efficiency (EQE) of 11.3%, which is about 30 times that of naphthyl-substituted counterpart with maximum EQE of 0.38%, shedding light on the importance of high triplet energy level of donor moiety on realizing TADF effect and high device efficiency for through-space charge transfer polymer.     

An efficient goal‐based reduced order model approach for targeted adaptive observations

An efficient adjoint sensitivity technique for optimally collecting targeted observations is presented. The targeting technique incorporates dynamical information from the numerical model predictions to identify when, where and what types of observations would provide the greatest improvement to specific model forecasts at a future time. A functional (goal) is defined to measure what is considered important in modelling problems. The adjoint sensitivity technique is used to identify the impact of observations on the predictive accuracy of the functional, then placing the sensors at the locations with high impacts. The adaptive (goal) observation technique developed here has the following features: (i) over existing targeted observation techniques, its novelty lies in that the interpolation error of numerical results is introduced to the functional (goal), which ensures the measurements are a distance apart; (ii) the use of proper orthogonal decomposition (POD) and reduced order modelling for both the forward and backward simulations, thus reducing the computational cost; and (iii) the use of unstructured meshes. The targeted adaptive observation technique is developed here within an unstructured mesh finite element model (Fluidity). In this work, a POD reduced order modelling is used to form the reduced order forward model by projecting the original complex model from a high dimensional space onto a reduced order space. The reduced order adjoint model is then constructed directly from the reduced order forward model. This efficient adaptive observation technique has been validated with two test cases: a model of an ocean gyre and a model of 2D urban street canyon flows. Copyright © 2016 John Wiley & Sons, Ltd.     

Quinoxaline and Pyrido[x,y-b]pyrazine-Based Emitters: Tuning Normal Fluorescence to Thermally Activated Delayed Fluorescence and Emitting Color over the Entire Visible-Light Range

Quinoxaline (Q), pyrido[2,3-b]pyrazine (PP) and pyrido[3,4-b]pyrazine (iPP) are used as electron acceptors (A) to design a series of D–π–A-type light-emitting materials with different donor (D) groups. By adjusting the molecular torsion angles through changing D from carbazole (Cz) to 10-dimethylacridine (DMAC) or 10H-phenoxazine (PXZ) for a fixed A, the luminescence is tuned from normal fluorescence to thermally activated delayed fluorescence (TADF). By gradually enhancing the intramolecular charge-transfer extent through combining different D and A, the emission color is continuously and regularly tuned from pure blue to orange–red. Organic light-emitting diodes (OLEDs) containing these compounds as doped emitters exhibit bright electroluminescence with emission colors covering the entire visible-light range. An external quantum efficiency (η_ext) of 1.2 % with excellent color coordinates of (0.16, 0.07) is obtained for the pure-blue OLED of Q-Cz. High η_ext values of 12.9 (35.9) to 16.7 % (51.9 cd A⁻¹) are realized in the green, yellow, and orange–red TADF OLEDs. All PP- and iPP-based TADF emitters exhibit superior efficiency stabilities to that of analogues of Q. This provides a practical strategy to tune the emission color of Q, PP, and iPP derivatives with the same molecular skeletons over the entire visible-light range.     

Through-Space Charge-Transfer Polynorbornenes with Fixed and Controllable Spatial Alignment of Donor and Acceptor for High-Efficiency Blue Thermally Activated Delayed Fluorescence

Through-space charge transfer polynorbornenes with fixed and controllable spatial alignment of donor and acceptor in edge-to-face/face-to-face stacking patterns are developed for achieving high-efficiency blue thermally activated delayed fluorescence (TADF). The alignment is realized by using the cis, exo-configuration of norbornene to confine donor and acceptor in close proximity, and utilizing orthogonal and dendritic structures of donors to provide either perpendicular or parallel stacking motif relative to acceptors. Compared to edge-to-face counterparts, polynorbornenes with face-to-face aligned donor and acceptor exhibit much larger oscillator strength and higher photoluminescence quantum yield. The resulting polymers exhibit deep blue (422 nm) to sky blue (482 nm) emission and TADF effect with reverse intersystem crossing rates of 0.4–5.9×10⁶ s⁻¹, giving the maximum external quantum efficiency of 18.8 % for non-doped blue organic light-emitting diodes by solution process.     

N‐doped cycloparaphenylenes: Tuning electronic properties for applications in thermally activated delayed fluorescence

We theoretically characterize a series of substituted cycloparaphenylene nanohoops to study the effect of incorporating an electron‐withdrawing group into their cyclic structure. We systematically vary the nature, position, and number of nitrogen‐containing acceptor groups in both neutral (pyridine) and charged forms (pyridinium and methylpyridinium) to provide insights into how this functionalization affects the structural, electronic, and optical properties of these systems. We focus also on the singlet‐triplet energy difference, with low values found, which might pave the way to further applications in the field of devices for light‐emitting applications providing a potential class of TADF‐based emitters.     

Convenient One-Pot Synthesis of 1,2,3,4-Thiatriazoles Towards a Novel Electron Acceptor for Highly-Efficient Thermally-Activated Delayed-Fluorescence Emitters

A novel and unexpected convenient one-pot synthesis of 1,2,3,4-thiatriazoles has been discovered while investigating the classical tetrazine “Pinner synthesis”. The synthetic route starts from commercially-available nitrile derivatives and gives good to high yields (51–80 %) with no need to isolate any thioacylating agents. The crucial impact of the solvent on the outcome of the modified “Pinner synthesis” is moreover examined and discussed. Using this new synthetic route, a novel donor-acceptor thiatriazole derivative has been prepared, which exhibits prominent thermally-activated delayed fluorescence (TADF) in both solution and film. The photoluminescence quantum yield (PLQY) in methylcyclohexane (MCH) and Zeonex (a cyclo olefin polymer) in oxygen-free conditions were determined to be 76 and 99 %, respectively. This work provides an efficient and practical synthetic approach to functionalized 1,2,3,4-thiatriazole derivatives, and will noticeably facilitate the application of 1,2,3,4-thiatriazole as an electron acceptor in organic electronics.     

Synthesis,aggregation-induced emission and thermally activated delayed fluorescence properties of two new compounds based on phenylethene,carbazole and 9,9′,10,10′-tetraoxidethianthrene

In the text, two luminescent materials ECPPTT and ECDPTT, have been designed and synthesized by integrating tetraphenyl/triphenyl-ethene(TPE/TrPE), carbazole group and thianthrene-9,9,10,10-tetraoxide unit. ECPPTT and ECDPTT possess obvious AIE and TADF capabilities, and show good thermal stability in their thin film of 240 °C and 262 °C, respectively. Non-doped organic light emitting diodes(OLED) using ECPPTT and ECDPTT as emission layer are prepared and exhibit blue-green and green emission color with peaks at 494, 517 nm, respectively. The non-doped OLED based on ECPPTT provides good peak EL efficiencies of 3.437 cdA^-1 and 10090cdm^-2; while non-doped OLED fabricated with ECDPTT affords a maximum current efficiency and a maximum luminance of 2.478 cdA^-1 and 7561cdm^-2. These results have demonstrated the feasibility of combing AIE and TADF units to design new molecules.     

Stochastic Nicholson’s blowflies delayed differential equations

In this paper, we consider a class of stochastic Nicholson’s blowflies delayed differential equations. Firstly, we obtain the existence and uniqueness of the global positive solution with nonnegative initial conditions. Then the ultimate boundedness in mean of solution is derived under the same condition. Moreover, we estimate the sample Lyapunov exponent of the solution, which is less than a positive constant. In the end, an example with its numerical simulations is carried out to validate the analytical results.     

Double stabilities of pullback random attractors for stochastic delayed p-Laplacian equations

We provide a method to study the double stabilities of a pullback random attractor (PRA) generated from a stochastic partial differential equation (PDE) with delays, such a PRA is actually a family of compact random sets A_ϱ(t,·), where t is the current time and ϱ is the memory time. We study its longtime stability, which means the attractor semiconverges to a compact set as the current time tends to minus infinity, and also its zero-memory stability, which means the delayed attractor semiconverges to the nondelayed attractor as the memory time tends to zero. The stochastic nonautonomous p-Laplacian equation with variable delays on an unbounded domain will be applied to illustrate the method and some suitable assumptions about the nonlinearity and time-dependent delayed forces can ensure existence, backward compactness, and double stabilities of a PRA.     

Synchronization for stochastic hybrid coupled controlled systems with Lévy noise

In this paper, synchronization for stochastic hybrid-delayed coupled systems with Lévy noise on a network (SHDCLN) is investigated via aperiodically intermittent control. Here time delays, Markovian switching and Lévy noise are considered on a network simultaneously for the first time. After that, by means of Lyapunov method, graph theory, and some techniques of inequality, some sufficient conditions are derived to guarantee the synchronization for SHDCLN. In addition, the designed range of aperiodically intermittent controller parameters is shown. Meanwhile, the coupling strength and the perturbed intensity of noise have a great impact on the intensity of control. Then, we investigate synchronization for stochastic hybrid delayed Chua's circuits with Lévy noise on a network as a practical application of our theoretical results. Finally, a numerical example is given to illustrate the effectiveness of the theoretical results.