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A new red-emitting CPL/TADF derivative is reported. A monomeric form is compared to its chiral dimeric counterpart to unravel the impact of dimerization on TADF properties. Circularly polarized fluorescence and phosphorescence are also investigated.

Plating efficiencies of cells before and after treatment with siRNAs and XAV-939, stimulation with Wnt-3a, overexpression of mutated β-catenin (S33Y) and SW1463 becoming radiation resistant. (A) Plating efficiencies for RT, (B) plating efficiencies for CRT.

Western blot analysis of (A) SW480, (B) SW837, and (C) RPE-1 cells after exposure to various doses of XAV-939 and DMSO as negative control.

Supplementary Figure and Table Legends

Activation of Wnt/β-catenin signaling plays a central role in the development and progression of colorectal cancer. The Wnt-transcription factor, TCF7L2, is overexpressed in primary rectal cancers that are resistant to chemoradiotherapy and TCF7L2 mediates resistance to chemoradiotherapy. However, it is unclear whether the resistance is mediated by a TCF7L2 inherent mechanism or Wnt/β-catenin signaling in general. Here, inhibition of β-catenin by siRNAs or a small-molecule inhibitor (XAV-939) resulted in sensitization of colorectal cancer cells to chemoradiotherapy. To investigate the potential role of Wnt/β-catenin signaling in controlling therapeutic responsiveness, nontumorigenic RPE-1 cells were stimulated with Wnt-3a, a physiologic ligand of Frizzled receptors, which increased resistance to chemoradiotherapy. This effect could be recapitulated by overexpression of a degradation-resistant mutant of β-catenin (S33Y), also boosting resistance of RPE-1 cells to chemoradiotherapy, which was, conversely, abrogated by siRNA-mediated silencing of β-catenin. Consistent with these findings, higher expression levels of active β-catenin were observed as well as increased TCF/LEF reporter activity in SW1463 cells that evolved radiation resistance due to repeated radiation treatment. Global gene expression profiling identified several altered pathways, including PPAR signaling and other metabolic pathways, associated with cellular response to radiation. In summary, aberrant activation of Wnt/β-catenin signaling not only regulates the development and progression of colorectal cancer, but also mediates resistance of rectal cancers to chemoradiotherapy.Implications: Targeting Wnt/β-catenin signaling or one of the downstream pathways represents a promising strategy to increase response to chemoradiotherapy. Mol Cancer Res; 15(11); 1481–90. ©2017 AACR.

The orientation of the emissive dipoles in thin-film devices is important since it strongly affects the light outcoupling and thereby the device emission efficiency. The light-emitting electrochemical cell (LEC) is particularly interesting in this context because its emissive dipoles are located in a high electric-field p-n junction, which is formed in situ by redistribution of bulky ions. This implies that the dipole orientation could be distinctly different in the driven LEC compared to the pristine device. This study develops the destructive-interference microcavity method for the accurate in situ determination of the orientation of the emissive dipoles during LEC operation and apply it on a common LEC device comprising an amorphous conjugated polymer termed Super Yellow as the emitter. It is found that ≈95% of the emissive dipoles are oriented in the horizontal direction with respect to the thin-film plane in both the pristine LEC and during steady-state light emission. This finding is attractive since it enables for efficient outcoupling of the generated photons, and interesting because it shows that a horizontal orientation of the emissive dipoles can remain despite the existence of a strong perpendicular electric field and the nearby motion of bulky ions during LEC operation.

Wavelength-discriminating systems typically consist of heavy benchtop-based instruments, comprising diffractive optics, moving parts, and adjacent detectors. For simple wavelength measurements, such as lab-on-chip light source calibration or laser wavelength tracking, which do not require polychromatic analysis and cannot handle bulky spectroscopy instruments, lightweight, easy-to-process, and flexible single-pixel devices are attracting increasing attention. Here, a device is proposed for monotonously transforming wavelength information into the time domain with room-temperature phosphorescence at the heart of its functionality, which demonstrates a resolution down to 1 nm and below. It is solution-processed from a single host-guest system comprising organic room-temperature phosphors and colloidal quantum dots. The share of excited triplet states within the photoluminescent layer is dependent on the excitation wavelength and determines the afterglow intensity of the film, which is tracked by a simple photodetector. Finally, an all-organic thin-film wavelength sensor and two applications are demonstrated where this novel measurement concept successfully replaces a full spectrometer.

Materials exhibiting thermally activated delayed fluorescence (TADF) have been extensively explored in the last decade. These emitters have great potential of being used in organic light-emitting diodes because they allow for high quantum efficiencies by utilizing triplet states via reverse intersystem crossing. In small molecules, this is done by spatially separating the highest occupied molecular orbital from the lowest unoccupied molecular orbital, forming an intramolecular charge-transfer (iCT) state and leading to a small energy difference between lowest excited singlet and triplet states (ΔEST). However, in polymer emitters, this is harder to achieve, and typical strategies usually include adding known TADF units as sidechains onto a polymer backbone. In a previous work, we proposed an alternative way to achieve a TADF polymer by repeating a non-TADF unit, polymerizing it via electron-donating carbazole moieties. The extended conjugation on the backbone reduced the ΔEST and allowed for an efficient TADF polymer. In this work, we present a more in-depth study of the shift from a non-TADF monomer to TADF oligomers. The monomer shows non-TADF emission, and we find the delayed emission to be of triplet-triplet annihilation origin. An iCT state is formed already in the dimer, leading to a much more efficient TADF emission. This is confirmed by an almost two-fold increase of photoluminescence quantum yield, a decrease in the delayed luminescence lifetime, and the respective spectral lineshapes of the molecules.

Semiconducting polymers that feature thermally activated delayed fluorescence (TADF) can deliver a much desired combination of high-efficiency and metal-free electroluminescence and cost-efficient solution-based fabrication. A TADF polymer is thus a very good fit for the emitting compound in light-emitting electrochemical cells (LECs) because the commonly employed air-stabile and few-layer LEC architecture is well suited for such solution-based fabrication. Herein we report on the first LEC device based on a TADF polymer as the emitting species, which delivers a luminance of 96 cd m–2 at 4 V and a current efficacy of 1.4 cd A–1 and >600 cd m–2 at 6 V, which is competitive with the performance of multilayer organic light-emitting diodes based on the same TADF polymer. We further utilize the established sensitivity of the emission of the TADF polymer to its environment to draw conclusions on the exciton populations in host-guest and host-free TADF LEC devices. Originally included in thesis in manuscript form.

Emitters showing thermally activated delayed fluorescence (TADF) in electroluminescent devices rely on efficient reverse intersystem crossing (rISC) arising from small thermal activation barriers between the lowest excited triplet and singlet manifolds. A small donor–acceptor compound consisting of a demethylacridine donor and a methylbenzoate acceptor group is used as a model TADF emitter. The spectroscopic signatures of this system are characterized using a combination of photoluminescence and photoluminescence excitation, and the photoluminescence decay dynamics are recorded between delays of 2 ns and 20 ms. Above T = 200 K, our data provide convincing evidence for TADF at intermediate delays in the microsecond range, whereas triplet–triplet annihilation and slow triplet decay at later times can be observed over the entire temperature range from T = 80 K to room temperature. Moreover, close to room temperature, we find a second and faster up-conversion mechanism, tentatively assigned to reverse internal conversion between different triplet configurations. An interpretation of these experimental findings requires a calculation of the deformation patterns and potential minima of several electronic configurations. This task is performed with a range-separated hybrid functional, outperforming standard density functionals or global hybrids. In particular, the systematic underestimation of the energy of charge transfer (CT) states with respect to local excitations within the constituting chromophores is replaced by more reliable transition energies for both kinds of excitations. Hence, several absorption and emission features can be assigned unambiguously, and the observed activation barriers for rISC and reverse internal conversion correspond to calculated energy differences between the potential surfaces in different electronic configurations.

Electrochromic devices (ECDs) have emerged as a unique class of optoelectronic devices for the development of smart windows. However, current ECDs typically suffer from low coloration efficiency (CE) and high energy consumption, which have thus hindered their practical applications, especially as components in solar-powered EC windows. Here, the high-performance ECDs with a fully crystalline viologen-immobilized 2D polymer (V2DP) thin film as the color-switching layer is demonstrated. The high density of vertically oriented pore channels (pore size approximate to 4.5 nm; pore density approximate to 5.8 x 1016 m-2) in the synthetic V2DP film enables high utilization of redox-active viologen moieties and benefits for Li+ ion diffusion/transport. As a result, the as-fabricated ECDs achieve a rapid switching speed (coloration, 2.8 s; bleaching, 1.2 s), and a high CE (989 cm2 C-1, and low energy consumption (21.1 µW cm-2). Moreover, it is managed to fabricate transmission-tunable, self-sustainable EC window prototypes by vertically integrating the V2DP ECDs with transparent solar cells. This work sheds light on designing electroactive 2D polymers with molecular precision for optoelectronics and paves a practical route toward developing self-powered EC windows to offset the electricity consumption of buildings.

Charge injection from electrodes into doped organic films is a widespread technology used in the majority of state-of-the-art organic semiconductor devices. Although such interfaces are commonly considered to form Ohmic contacts via strong band bending, an experiment that directly measures the contact resistance has not yet been demonstrated. In this study, we use a simple metal/doped organic semiconductor/metal stack and study its voltage-dependent resistance. A transport layer thickness variation proves that the presented experiment gains direct access to the contact resistance of the device. We can quantify that for an operating current density of 10mA/cm2 the investigated material system exhibits a voltage drop over the metal/organic interface of about 200mV, which can be reduced by more than one order of magnitude when employing an additional injection layer. The presented experiment proposes a simple strategy to measure the contact resistance between any metal and doped organic film without applying numerical tools or elaborate techniques. Furthermore, the simplistic device architecture allows for very high, homogeneous, and tunable electric fields within the organic layer, which enables a clear investigation of the Poole-Frenkel effect.

Organic thin-film lasers gain interest as potential light sources for application in diverse fields. With the current development, they hold variety of benefits such as: low-cost, high-performance, and color-tunability. Meanwhile, the production is not complicated because both the resonator and the gain medium can be assembled by solution-processable organic materials. To our knowledge, information about using poly(methyl methacrylate) (PMMA) as a matrix for organic dye lasers was insubstantial. Herein, the feasibility of using organic dye-doped PMMA as an organic dye laser was tested. Six different sample designs were introduced to find out the best sample model. The most optimum result was displayed by the sample design, in which the gain medium was sandwiched between the substrate and the photoresist layer with grating structure. The impact of dye concentration and grating period on peak wavelength was also investigated, which resulted in a shift of 6 nm and 25 nm, respectively. Moreover, there were in total six various organic dyes that could function well with PMMA to collectively perform as ‘organic dye lasers’, and they emitted in the range of 572 nm to 609 nm. Besides, one of the samples was used as a sensor platform. For instance, it was used to detect the concentration of sugar solutions.

Herein, a simple way of tuning the optical and structural properties of porphyrin‐based hydrogen‐bonded organic frameworks (HOFs) is reported. By inserting transition metal ions into the porphyrin cores of GTUB‐5 (p‐H8‐TPPA (5,10,15,20‐Tetrakis[p‐phenylphosphonic acid] HOF), the authors show that it is possible to generate HOFs with different band gaps, photoluminescence (PL) life times, and textural properties. The band gaps of the resulting HOFs (viz., Cu‐, Ni‐, Pd‐, and Zn‐GTUB‐5) are measured by diffuse reflectance and PL spectroscopy, as well as calculated via DFT, and the PL lifetimes are measured. Across the series, the band gaps vary over a narrow range from 1.37 to 1.62 eV, while the PL lifetimes vary over a wide range from 2.3 to 83 ns. These differences ultimately arise from metal‐induced structural changes, viz., changes in the metal‐to‐nitrogen distances, number of hydrogen bonds, and pore volumes. DFT reveals that the band gaps of Cu‐, Zn‐, and Pd‐ GTUB‐5 are governed by highest occupied/lowest unoccupied crystal orbitals (HOCO/LUCO) composed of π‐ orbitals on the porphyrin linkers, while that of Ni‐GTUB‐5 is governed by a HOCO and LUCO composed of Ni dorbitals. Overall, our findings show that metal‐insertion can be used to optimize HOFs for optoelectronics and small‐molecule capture applications.

All inorganic lead halide perovskite nanocrystals (PNCs) typically suffer from poor stability against moisture and UV radiation as well as degradation during thermal treatment. The stability of PNC...

p-Type molecular doping of organic materials with high ionization energies (IEs) of above 5.50 eV is still a challenge, limiting the use of doping in high-performance organic light-emitting diodes (OLEDs). Here, we investigate the molecular dopant hexacyano-trimethylene-cyclopropane (CN6-CP) with a high electron affinity of 5.87 eV as p-dopant in OLEDs. We show that CN6-CP can be used not only as a dopant in the traditional hole transport material 4,4'-cyclohexylidenebis[ N, N-bis(4-methylphenyl)benzenamine] (TAPC, IE = 5.50 eV) but also effectively dopes the host material tris(4-carbazoyl-9-ylphenyl)amine (TCTA, IE = 5.85 eV), reaching a conductivity of 1.86 × 10

Organic electronic devices such as light-emitting diodes, solar cells or rectifying diodes normally have a sandwich layer architecture stacked between the electrodes in a crossbar layout. Often however, the side effects of operating the devices in such an arrangement are either ignored or give rise to misinterpretations regarding the device performance or layer quality. For the sake of simplicity, device currents are typically assumed to exclusively flow in the direction vertical to the substrate, even though the conductivity of doped organic layers is high and gives rise to significant lateral current flows. Here, we study the vertical and lateral charge up along the n-doped and the p-doped layers as well as the resulting capacitance increase of charging the intrinsic layer outside the active area. We observe that controlling such lateral charging by structuring the doped layers can reduce the leakage current dramatically. We employ impedance spectroscopy to investigate the lateral charging responsibility for the capacitance increase at low frequencies. Modeling of the devices by a distributed RC circuit model yields information about the thickness, the conductivity, and the corresponding activation energy of both, the n-doped and the p-doped layers, simultaneously. We demonstrate that the capacitive effects from lateral charging can easily be misinterpreted as trap states in capacitance frequency characteristics. However, correct analysis with the proposed model actually yields rich and detailed post-fabrication information which can be utilized in device failure and degradation tests. Moreover, our results will aid the design and characterization of new electronic devices where lateral charge flow is part of the device concept.

For almost 70 years, Forster resonance energy transfer (FRET) has been investigated, implemented into nowadays experimental nanoscience techniques, and considered in a manifold of optics, photonics, and optoelectronics applications. Here, we demonstrate for the first time simultaneous and efficient energy transfer from both donating singlet and triplet states of a single photoluminescent molecular species. Using a biluminescent donor that can emit with high yield from both excited states at room temperature allows application of the FRET framework to such a bimodal system. It serves as an exclusive model system where the spatial origin of energy transfer is exactly the same for both donating spin states involved. Of paramount significance are the facts that both transfers can easily be observed by eye and that Forster theory is successfully applied to state lifetimes spanning over 8 orders of magnitude.

The efficiency of organic light-emitting diodes that utilize the principle of thermally activated delayed fluorescence (TADF) depends sensitively on the host material in which the TADF emitter molecules (guests) are embedded. Potential loss processes are "deconfinement,"the transfer of excitons from the guest to the host, and "dissociation,"the formation of intermolecular charge-transfer states. We investigate how both processes can be suppressed by studying the photoluminescence efficiency, emission spectrum, and time-resolved emission intensity of eight thin-film systems in which 5 mol. % of the sky-blue TADF emitter 4-carbazolyl-methylphthalimide (abbreviated here as CzPIMe) is embedded in various host materials. Deconfinement is found to be entirely suppressed if the triplet energy of the host is 0.25 eV or more above that of the guest. For systems allowing for deconfinement, the dependence on the energy difference is consistent with a recent theoretical analysis [C. Hauenstein et al., J. Appl. Phys. 128, 075501 (2020)]. Dissociation, due to hole transfer to a host molecule, is found to be suppressed if the host's highest occupied molecular orbital energy is not more than about 0.2 eV higher than that of the guest. Otherwise, we observe an efficiency loss, a spectral redshift, and the disappearance of distinct prompt and delayed emission regimes. A comprehensive rate-equation model is developed from which we study the sensitivity of these observations to the energy level structure, the intermolecular interaction rates, and the photophysical rates that follow from a fit to the experimental data for the CzPIMe:TCTA [tris (4 - carbazoyl - 9 - ylphenyl) amine] system.

Hierarchical textures are researched experimentally and by optical simulations in the role of external outcoupling solution for OLEDs. Their full outcoupling potential, limiting factors and pathways for further increase in outcoupling are addressed.

Angle-resolved photoluminescence spectroscopy is a powerful tool for investigation of the properties of light-emitting thin-film structures. For instance, it can reveal information about the orientation of the transition dipole moment in organic emission layers, which is one of the most important parameters defining the efficiency of organic light-emitting diodes. In this work, a refinement of one of the main experimental configurations utilized for such orientation measurements is presented. The technique is based on a step-by-step rotation of the optically excited layer with respect to the detector. By attaching the sample to a large glass half cylinder, the light initially trapped in the substrate can be extracted. It is shown that by inserting two additional optical lenses between the half cylinder and the detector, the signal-to-noise ratio can be improved by about one order of magnitude. A ray-optics model is derived that describes the light propagation in the macroscopic setup and enables us to characterize the impact of deviations from theoretical ideal measurement configurations. The numerical predictions are experimentally validated analyzing quantum-dot emission layers as an isotropic reference and established organic emitter molecules with well-known orientation values.

A spin-flip from a triplet to a singlet excited state, that is, reverse intersystem crossing (RISC), is an attractive route for improving light emission in organic light-emitting diodes, as shown by devices using thermally activated delayed fluorescence (TADF). However, device stability and efficiency roll-off remain challenging issues that originate from a slow RISC rate (kRISC). Here, we report a TADF molecule with multiple donor units that form charge-resonance-type hybrid triplet states leading to a small singlet–triplet energy splitting, large spin–orbit couplings, and a dense manifold of triplet states energetically close to the singlets. The kRISC in our TADF molecule is as fast as 1.5 × 107 s−1, a value some two orders of magnitude higher than typical TADF emitters. Organic light-emitting diodes based on this molecule exhibit good stability (estimated T90 about 600 h for 1,000 cd m−2), high maximum external quantum efficiency (>29.3%) and low efficiency roll-off (

Interfaces between organic electron-donating (D) and electron-accepting (A) materials can show efficient free charge carrier generation upon illumination, enabling organic photovoltaic devices and photodetectors with photon to electron conversion yields approaching 100%. Recently, organic light-emitting diodes (OLEDs) based on charge transfer (CT) (or exciplex) emission occurring at such D-A interfaces have been shown to exhibit high electroluminescence external quantum yields (EQEEL). However, no organic D-A combination with both a high EQEEL, as well as a high free carrier generation yield has been discovered so far. Such a system would result in significantly higher operating voltages in organic solar cells, reduced dark current in organic photodetectors, and reduced driving voltages for OLEDs.