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A series of windmill-shape heterocyclic molecules containing three N-B←N units, TBN and its derivatives, with quasi-planar C 3 symmetric backbone, are synthesized. The parent TBN exhibits a strongly allowed, doubly degenerate lowest excited state but suffers from very low fluorescence, due to very fast nonradiative decay rate through a conical intersection (CI) as revealed by femtosecond transient absorption spectroscopy and quantum-chemical calculations. Introducing peripheral phenyl- or thienyl-groups (Ph-TBN or Th-TBN) induces pronounced bathochromic shifts and enhances fluorescence, which is beneficial from inhibited nonradiative pathway by the increased energy barriers to access the CI at excited state. The understanding of this rather uncommon behaviour may open routes for the design of novel fluorescence materials., (© 2024 Wiley-VCH GmbH.)

We showcase herein organic crystalline solid solutions (CSSs) based on the simplest polycyclic aromatic hydrocarbon (PAH) scaffold, naphthalene, stabilized by dispersion forces induced by adamantane substitution. High thermal stability of the host and guest molecules synthesized by cross-coupling of dibromonaphthalene derivatives and 4-(1-adamantyl)phenyl boronic ester enabled formation of crystals by sublimation. We could generate binary monocrystalline solid solution systems proven by X-ray crystallography, the first system of designed CSSs stabilized exclusively via dispersion forces with structural evidence. These observations are additionally supported by lattice energy calculations and spectroscopic examinations. For the generation of CSSs, it is of utmost importance that the host and guest molecules have similar lattice energies and spatial compatibility. We anticipate that the thermostable organic CSS design demonstrated herein would be beneficial for functional materials and further investigation towards materials with unique properties., (© 2024 The Authors. ChemPlusChem published by Wiley-VCH GmbH.)

We investigated the role of alpha in the suppression of attention capture by salient but to-be-suppressed (negative and nonpredictive) color cues, expecting a potential boosting effect of alpha-rhythmic entrainment on feature-specific cue suppression. We did so by presenting a rhythmically flickering visual bar of 10 Hz before the cue - either on the cue's side or opposite the cue -while an arrhythmically flickering visual bar was presented on the respective other side. We hypothesized that rhythmic entrainment at cue location could enhance the suppression of the cue. Testing 27 participants ranging from 18 to 39 years of age, we found both behavioral and electrophysiological evidence of suppression: Search times for a target at a negatively cued location were delayed relative to a target away from the cued location (inverse validity effects). In addition, an event-related potential indicative for suppression (the Distractor Positivity, Pd) was observed following rhythmic but not arrhythmic stimulation, indicating that suppression was boosted by the stimulation. This was also echoed in higher spectral power and intertrial phase coherence of EEG at rhythmically versus arrhythmically stimulated electrode sites, albeit only at the second harmonic (20 Hz), but not at the stimulation frequency. In addition, inverse validity effects were not modulated by rhythmic entrainment congruent with the cue side. Hence, we propose that rhythmic visual stimulation in the alpha range could support suppression, though behavioral evidence remains elusive, in contrast to electrophysiological findings., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2024 Szaszkó, Habeler, Forstinger, Pomper, Scheftner, Stolte, Grüner and Ansorge.)

Simulation is a crucial tool for the evaluation and comparison of statistical methods. How to design fair and neutral simulation studies is therefore of great interest for both researchers developing new methods and practitioners confronted with the choice of the most suitable method. The term simulation usually refers to parametric simulation, that is, computer experiments using artificial data made up of pseudo-random numbers. Plasmode simulation, that is, computer experiments using the combination of resampling feature data from a real-life dataset and generating the target variable with a known user-selected outcome-generating model, is an alternative that is often claimed to produce more realistic data. We compare parametric and Plasmode simulation for the example of estimating the mean squared error (MSE) of the least squares estimator (LSE) in linear regression. If the true underlying data-generating process (DGP) and the outcome-generating model (OGM) were known, parametric simulation would obviously be the best choice in terms of estimating the MSE well. However, in reality, both are usually unknown, so researchers have to make assumptions: in Plasmode simulation studies for the OGM, in parametric simulation for both DGP and OGM. Most likely, these assumptions do not exactly reflect the truth. Here, we aim to find out how assumptions deviating from the true DGP and the true OGM affect the performance of parametric and Plasmode simulations in the context of MSE estimation for the LSE and in which situations which simulation type is preferable. Our results suggest that the preferable simulation method depends on many factors, including the number of features, and on how and to what extent the assumptions of a parametric simulation differ from the true DGP. Also, the resampling strategy used for Plasmode influences the results. In particular, subsampling with a small sampling proportion can be recommended., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Stolte et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Vapor sensors with both high sensitivity and broad detection range are technically challenging yet highly desirable for widespread chemical sensing applications in diverse environments. Generally, an increased surface-to-volume ratio can effectively enhance the sensitivity to low concentrations, but often with the trade-off of a constrained sensing range. Here, an approach is demonstrated for NH 3 sensor arrays with an unprecedentedly broad sensing range by introducing controllable steps on the surface of an n-type single crystal. Step edges, serving as adsorption sites with electron-deficient properties, are well-defined, discrete, and electronically active. NH 3 molecules selectively adsorb at the step edges and nearly eliminate known trap-like character, which is demonstrated by surface potential imaging. Consequently, the strategy can significantly boost the sensitivity of two-terminal NH 3 resistance sensors on thin crystals with a few steps while simultaneously enhancing the tolerance on thick crystals with dense steps. Incorporation of these crystals into parallel sensor arrays results in ppb-to-% level detection range and a convenient linear relation between sheet conductance and semi-log NH 3 concentration, allowing for the precise localization of vapor leakage. In general, the results suggest new opportunities for defect engineering of organic semiconductor crystal surfaces for purposeful vapor or chemical sensing., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

Past research suggests a continuity between perception and memory, as reflected in influences of orienting of spatial attention by cues presented after a visual target offset (post-target cues) on target perception. Conducting two experiments, we tested and confirmed this claim. Our study revealed an elevated reliance on post-target cues for target detection with diminishing target visibility, leading to better performance in validly versus invalidly cued trials, indicative of contrast gain. We demonstrated this post-target cueing impact on target perception without a postcue response prompt, meaning that our results truly reflected a continuity between perception and memory rather than a task-specific impact of having to memorize the target due to a response prompt. While previous studies found an improvement in accuracy through valid compared to invalid cues using liminal targets, in Experiment 1, we further showed an influence of attention on participants' response time by the post-target cues with cues presented away from a clearly visible target. This suggests that visual interactions at the target location provided no better explanation of post-target cueing effects. Our results generalize prior research with liminal targets and confirm the view of a perception-memory continuum so that visual target processing is not shielded against visuospatial orienting of attention elicited by events following the offset of the visual target.

In the current study, we used abrupt-onset distractors similar and dissimilar in luminance to the target of a smooth pursuit eye-movement to test if abrupt-onset distractors capture attention in a top-down or bottom-up fashion while the eyes track a moving object. Abrupt onset distractors were presented at different positions relative to the current position of a pursuit target during the closed-loop phase of smooth pursuit. Across experiments, we varied the duration of the distractors, their motion direction, and task-relevance. We found that abrupt-onset distractors decreased the gain of horizontally directed smooth-pursuit eye-movements. This effect, however, was independent of the similarity in luminance between distractor and target. In addition, distracting effects on horizontal gain were the same, regardless of the exact duration and position of the distractors, suggesting that capture was relatively unspecific and short-lived (Experiments 1 and 2). This was different with distractors moving in a vertical direction, perpendicular to the horizontally moving target. In line with past findings, these distractors caused suppression of vertical gain (Experiment 3). Finally, making distractors task-relevant by asking observers to report distractor positions increased the pursuit gain effect of the distractors. This effect was also independent of target-distractor similarity (Experiment 4). In conclusion, the results suggest that a strong location signal exerted by the pursuit targets led to very brief and largely location-unspecific interference through the abrupt onsets and that this interference was bottom-up, implying that the control of smooth pursuit was independent of other target features besides its motion signal., (© 2023 The Authors. Psychophysiology published by Wiley Periodicals LLC on behalf of Society for Psychophysiological Research.)

Self-assembly versus complexation with polycyclic aromatic hydrocarbon (PAH) guest molecules is studied for a series of perylene bisimides (PBIs). Bulky imide substituents at the PBI guide their self-assembly into dimer aggregates with null-type exciton coupling. Host-guest titration experiments with perylene and triphenylene PAHs afford 1 : 1 and 1 : 2 complexes whose properties are studied by single crystal X-ray analysis and UV/Vis and fluorescence spectroscopy.

Five chiral squaraine dimers were synthesized by fusing chiral indolenine semisquaraines with three different benzobisthiazole bridges. The thereby created squaraine dimers show a strong splitting of the lowest energy absorption bands caused by exciton coupling. The intensities of the two exciton transitions and the energetic splitting depend on the angle of the two squaraine moieties within the chromophore dimer. The electric circular dichroism spectra of the dimers show intense Cotton effects whose sign depends on the used squaraine chromophores. Sizable anisotropies g abs of up to 2.6 × 10 -3 could be obtained. TD-DFT calculations were used to partition the rotational strength into the three Rosenfeld terms where the electric-magnetic coupling turned out to be the dominant contribution while the exciton chirality term is much smaller. This is because the chromophore dimers are essentially planar but the angle between the electric transition dipole moment of one squaraine and the magnetic transition dipole moment of the other squaraine strongly deviates from 90°, which makes the dot product between the two moment vectors and, thus, the rotational strength substantial.

The Sensory Gating Inventory (SGI) is an established self-report questionnaire that is used to assess the capacity for filtering redundant or irrelevant environmental stimuli. Translation and cross-cultural validation of the SGI are necessary to make this tool available to Dutch speaking populations. This study, therefore, aimed to design and validate a Dutch Sensory Gating Inventory (D-SGI). To this end, a forward-backward translation was performed and 469 native Dutch speakers filled in the questionnaire. A confirmatory factor analysis assessed the psychometric properties of the D-SGI. Additionally, test-retest reliability was measured. Results confirmed satisfactory similarity between the original English SGI and the D-SGI in terms of psychometric properties for the factor structure. Internal consistency and discriminant validity were also satisfactory. Overall test-retest reliability was excellent (ICC = 0.91, p  < 0.001, 95% CI [0.87-0.93]). These findings confirm that the D-SGI is a psychometrically sound self-report measure that allows assessing the phenomenological dimensions of sensory gating in Dutch. Moreover, the D-SGI is publicly available. This establishes the D-SGI as a new tool for the assessment of sensory gating dimensions in general- and clinical Dutch speaking populations.

Chiral polycyclic aromatic hydrocarbons can be tailored for next-generation photonic materials by carefully designing their molecular as well as supramolecular architectures. Hence, excitonic coupling can boost the chiroptical response in extended aggregates but is still challenging to achieve by pure self-assembly. Whereas most reports on these potential materials cover the UV and visible spectral range, systems in the near infrared (NIR) are underdeveloped. We report a new quaterrylene bisimide derivative with a conformationally stable twisted π-backbone enabled by the sterical congestion of a fourfold bay -arylation. Rendering the π-subplanes accessible by small imide substituents allows for a slip-stacked chiral arrangement by kinetic self-assembly in low polarity solvents. The well dispersed solid-state aggregate reveals a sharp optical signature of strong J-type excitonic coupling in both absorption (897 nm) and emission (912 nm) far in the NIR region and reaches absorption dissymmetry factors up to 1.1 × 10 -2 . The structural elucidation was achieved by atomic force microscopy and single-crystal X-ray analysis which we combined to derive a structural model of a fourfold stranded enantiopure superhelix. We could deduce that the role of phenyl substituents is not only granting stable axial chirality but also guiding the chromophore into a chiral supramolecular arrangement needed for strong excitonic chirality.

Two [ n ]heliceno-bis(naphthalimides) 1 and 2 ( n = 5 and 6, respectively) where two electron-accepting naphthalimide moieties are attached at both ends of helicene core were synthesized by effective two-step strategy, and their enantiomers could be resolved by chiral stationary-phase high-performance liquid chromatography (HPLC). The single-crystal X-ray diffraction analysis of enantiopure fractions of 1 and 2 confirmed their helical structure, and together with experimental and calculated circular dichroism (CD) spectra, the absolute configuration was unambiguously assigned. Both 1 and 2 exhibit high molar extinction coefficients for the S 0 -S 1 transition and high fluorescence quantum yields (73% for 1 and 69% for 2 ), both being outstanding for helicene derivatives. The red circularly polarized luminescence (CPL) emission up to 615 nm for 2 with CPL brightness ( B ) up to 66.5 M CPL ) up to 66.5 M -1 cm -1 demonstrates its potential for applications in chiral optoelectronics. Time-dependent density functional theory (TD-DFT) calculations unambiguously showed that the large transition magnetic dipole moment | m | of 2 is responsible for its high absorbance dissymmetry ( g abs ) and luminescence dissymmetry ( g lum ) factor.

Perylene bisimide (PBI) dyes are known as red, maroon and black pigments, whose colors depend on the close π-π stacking arrangement. However, contrary to the luminescent monomers, deep-red and black PBI pigments are commonly non- or only weakly fluorescent due to (multiple) quenching pathways. Here, we introduce N-alkoxybenzyl substituted PBIs that contain close π stacking arrangement (exhibiting d π-π ≈ 3.5 Å, and longitudinal and transversal displacements of 3.1 Å and 1.3 Å); however, they afford deep-red emitters with solid-state fluorescence quantum yields (Φ F ) of up to 60%. Systematic photophysical and computational studies in solution and in the solid state reveal a sensitive interconversion of the PBI-centred locally excited state and a charge transfer state, which depends on the dihedral angle (θ) between the benzyl and alkoxy groups. This effectively controls the emission process, and enables high Φ F by circumventing the common quenching pathways commonly observed for perylene black analogues., (© 2023. The Author(s).)

Heavy-atom-containing clusters, nanocrystals, and other semiconductors can sensitize the triplet states of their surface-bonded chromophores, but the energy loss, such as nonradiative deactivation, often prevents the synergistic light emission in their solid-state coassemblies. Cocrystallization allows new combinations of molecules with complementary properties for achieving functionalities not available in single components. Here, the cocrystal formation that employs platinum(II) acetylacetonate (Pt(acac) 2 ) as a triplet sensitizer and electron-deficient 1,4,5,8-naphthalene diimides (NDIs) as organic phosphors is reported. The hybrid cocrystals exhibit room-temperature phosphorescence confined in the low-lying, long-lived triplet state of NDIs with photoluminescence (PL) quantum yield (Φ PL ) exceeding 25% and a phosphorescence lifetime (τ Ph ) of 156 µs. This remarkable PL property benefits from the noncovalent electronic and spin-orbital coupling between the constituents., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Human retina- and brain-inspired optoelectronic synapses, which integrate light detection and signal memory functions for data processing, have significant interest because of their potential applications for artificial vision technology. In nature, many animals such as mantis shrimp use polarized light information as well as scalar information including wavelength and intensity; however, a spectropolarimetric organic optoelectronic synapse has been seldom investigated. Herein, we report an organic synaptic phototransistor, consisting of a charge trapping liquid-crystalline perylene bisimide J-aggregate and a charge transporting crystalline dichlorinated naphthalene diimide, that can detect both wavelength and polarization information. The device shows persistent positive and negative photocurrents under low and high voltage conditions, respectively. Furthermore, the aligned organic heterostructure in the thin-film enables linearly polarized light to be absorbed with a dichroic ratio of 1.4 and 3.7 under transverse polarized blue and red light illumination, respectively. These features allow polarized light sensitive postsynaptic functions in the device. Consequently, a simple polarization imaging sensor array is successfully demonstrated using photonic synapses, which suggests that a supramolecular material is an important candidate for the development of spectropolarimetric neuromorphic vision systems.

Yamamoto homocoupling of two chiral oxindoles led to the atropo-diastereoselective formation of an axially chiral oxindole dimer. This building block served as the starting material for the syntheses of axially chiral squaraine and merocyanine chromophore dimers. These dimers show pronounced chiroptical properties, this is, outstandingly high ECD signals (Δ ε up to ca. 1500 M -1 cm -1 ) as a couplet with positive Cotton effect for the P -configuration around the biaryl axis and a negative Cotton effect for the M -configuration. All investigated dimers also exhibit pronounced circularly polarised emission with anisotropy values of ca. 10 -3 cgs. Time-dependent density functional calculations were used to analyse the three contributions (local one electron, electric-magnetic coupling, and exciton coupling) to the rotational strength applying the Rosenfeld equation to excitonically coupled chromophores. While the exciton coupling term proves to be the dominant one, the electric-magnetic coupling possesses the same sign and adds significantly to the total rotational strength owing to a favourable geometric arrangement of the two chromophores within the dimer., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A new class of perylene bisimide (PBI) derivatives is introduced by bridging 1,12- and 1,6,7,12-hydroxy functionalized bay positions with oxygen-carbon-oxygen linker(s). This functionalization rigidifies the inherently twisted bay-substituted perylene core to afford dyes of high stability and solubility that are characterized by vibronically well-resolved absorption and fluorescence spectra and intense yellow emission with quantum yields close to 100%.

Previous research on ADHD and ASD has mainly focused on the deficits associated with these conditions, but there is also evidence for strengths. Unfortunately, our understanding of potential strengths in neurodevelopmental conditions is limited. One particular strength, creativity, has been associated with both ADHD and ASD. However, the distinct presentations of both conditions beg the question whether ADHD and ASD associate with the same or different aspects of creativity. Therefore, the current study investigated the links between ADHD and ASD symptoms, creative thinking abilities, and creative achievements. To investigate the spectrum of ADHD and ASD symptoms, self-reported ADHD and ASD symptoms, convergent (Remote Associations Test) and divergent thinking (Alternative Uses Task) and creative achievements (Creative Achievement Questionnaire) were assessed in a self-reportedly healthy sample of adults ( n = 470). We performed correlation analysis to investigate the relation between ADHD/ASD symptoms and creativity measures. In a second phase of analysis, data from an adult ADHD case-control study ( n = 151) were added to investigate the association between ADHD symptoms and divergent thinking in individuals with and without a diagnosis of ADHD. Our analysis revealed that having more ADHD symptoms in the general population was associated with higher scores on all the outcome measures for divergent thinking (fluency, flexibility, and originality), but not for convergent thinking. Individuals with an ADHD diagnosis in the case-control sample also scored higher on measures of divergent thinking. Combining data of the population based and case-control studies showed that ADHD symptoms predict divergent thinking up to a certain level of symptoms. No significant associations were found between the total number of ASD symptoms and any of the creativity measures. However, explorative analyses showed interesting links between the ASD subdomains of problems with imagination and symptoms that relate to social difficulties. Our findings showed a link between ADHD symptoms and divergent thinking abilities that plateaus in the clinical spectrum of symptoms. For ASD symptoms, no relation was found with creativity measures. Increasing the knowledge about positive phenotypes associated with neurodevelopmental conditions and their symptom dimensions might aid psychoeducation, decrease stigmatization and improve quality of life of individuals living with such conditions., Competing Interests: BF has received educational speaking fees from Medice. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Stolte, Trindade-Pons, Vlaming, Jakobi, Franke, Kroesbergen, Baas and Hoogman.)

Graphene nanoribbons (GNRs) have the potential for next-generation functional devices. So far, GNRs with defined stereochemistry are rarely reported in literature and their optical response is usually bound to the ultraviolet or visible spectral region, while covering the near-infrared (NIR) regime is still challenging. Herein, we report two novel quaterrylene bisimides with either one- or twofold-twisted π-backbones enabled by the steric congestion of a fourfold bay arylation leading to an end-to-end twist of up to 76°. The strong interlocking effect of the π-stacked aryl substituents introduces a rigidification of the chromophore unambiguously proven by single-crystal X-ray analysis. This leads to unexpectedly strong NIR emissions at 862 and 903 nm with quantum yields of 1.5 and 0.9%, respectively, further ensuring high solubility as well as resolvable and highly stable atropo-enantiomers. Circular dichroism spectroscopy of these enantiopure chiral compounds reveals a strong Cotton effect Δε of up to 67 M -1 cm -1 centered far in the NIR region at 849 nm.

The current study investigated whether lower sensory and sensorimotor gating were related to higher levels of creativity and/or attentional difficulties in a natural population of primary school children (9- to 13-year-old). Gating abilities were measured with P50 suppression and prepulse inhibition of the startle reflex (PPI). The final sample included 65 participants in the P50 analyses and 37 participants in the PPI analyses. Our results showed that children with a high P50 amplitude to testing stimuli scored significantly higher on the divergent outcome measures of fluency and flexibility but not originality compared to children with a lower amplitude. No significant differences were found on any of the creativity measures when the sample was split on average PPI parameters. No significant differences in attention, as measured with a parent questionnaire, were found between children with low or high levels of sensory or sensorimotor gating. The data suggest that quantitative, but not qualitative measures of divergent thinking benefit from lower psychophysiological gating and that attentional difficulties stem from specific instead of general gating deficits. Future studies should take the effect of controlled attention into consideration., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Stolte, Oranje, Van Luit and Kroesbergen.)

Dye-dye interactions affect the optical and electronic properties in organic semiconductor films of light harvesting and detecting optoelectronic applications. This review elaborates how to tailor these properties of organic semiconductors for organic solar cells (OSCs) and organic photodiodes (OPDs). While these devices rely on similar materials, the demands for their optical properties are rather different, the former requiring a broad absorption spectrum spanning from the UV over visible up to the near-infrared region and the latter an ultra-narrow absorption spectrum at a specific, targeted wavelength. In order to design organic semiconductors satisfying these demands, fundamental insights on the relationship of optical properties are provided depending on molecular packing arrangement and the resultant electronic coupling thereof. Based on recent advancements in the theoretical understanding of intermolecular interactions between slip-stacked dyes, distinguishing classical J-aggregates with predominant long-range Coulomb coupling from charge transfer (CT)-mediated or -coupled J-aggregates, whose red-shifts are primarily governed by short-range orbital interactions, is suggested. Within this framework, the relationship between aggregate structure and functional properties of representative classes of dye aggregates is analyzed for the most advanced OSCs and wavelength-selective OPDs, providing important insights into the rational design of thin-film optoelectronic materials., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

A series of donor-acceptor (D-A) macrocyclic dyads consisting of an electron-poor perylene bisimide (PBI) π-scaffold bridged with electron-rich α-oligothiophenes bearing four, five, six and seven thiophene units between the two phenyl-imide substituents has been synthesized and characterized by steady-state UV/Vis absorption and fluorescence spectroscopy, cyclic and differential pulse voltammetry as well as transient absorption spectroscopy. Tying the oligothiophene strands in a conformationally fixed macrocyclic arrangement leads to a more rigid π-scaffold with vibronic fine structure in the respective absorption spectra. Electrochemical analysis disclosed charged state properties in solution which are strongly dependent on the degree of rigidification within the individual macrocycle. Investigation of the excited state dynamics revealed an oligothiophene bridge size-dependent fast charge transfer process for the macrocyclic dyads upon PBI subunit excitation., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Perylene-3,4:9,10-bis(dicarboximides) (PBIs) rank among the most important functional dyes and organic semiconductors, but only recently have their radical anions and dianions attracted interest for a variety of applications. Here, we systematically elucidate the functional properties (redox, absorption, and emission) of five PBI anions and dianions bearing different bay-substituents attached to the chromophore core. Cyclic voltammetry measurements reveal the influence of the substituents ranging from electron-withdrawing cyano to electron-donating phenoxy groups on the oxidation and reduction potentials that relate to the HOMO and LUMO levels ranging from -7.07 eV to -6.05 eV and -5.01 eV to -4.05 eV, respectively. Spectroelectrochemical studies reveal a significant number of intense absorption bands in the NIR-spectral range (750-1400 nm) for the radical anions, whereas the dianionic species are characterized by similar spectra to those for the neutral dyes, however being bathochromically shifted and with increased molar extinction coefficients of approximately 100 000 M -1 cm -1 . The increase of the transition dipole moment is up to 56% and accompanied by an almost cyanine-like red-shifted (by 300 nm) absorption spectrum for the most electron-poor tetracyanotetrachloro PBI. Whilst the outstanding fluorescence properties of the neutral PBIs are lost for the radical anions, an appreciable near-infrared (NIR) fluorescence with a quantum yield of up to 18% is revealed for the dianions by utilizing a custom-built flow-cell spectroelectrochemistry setup. Time-dependent density functional theory calculations help to assign the absorption bands to the respective electronic transitions.

In this study, a pig toilet was installed on an organic pig farm, which enabled pigs to use a lying area littered with straw and keep it clean. The pig toilet was separated into a defaecation area and a urination area and nursery pigs were trained to use the urination area by means of a rewarding system. A total of 24 piglets were weaned at 6-7 weeks of age and housed in the experimental system for four-week periods. Per trial, a group of four pigs was formed, and videos were recorded on two days per week (08:00 to 18:00). Direct observation was carried out in the first and last week of each trial. In total, 1500 eliminations were video-analysed. An individual pig had an average of 7.1 ± 1.4 defaecations and 4.8 ± 0.8 urinations per day. In total, 96.4% of all urinations and 97.4% of all defaecations were performed in the pig toilet. However, most urinations took place in the defaecation area as well (90.4%). Even if the training to spatially separate defecation and urination behaviour was not successful, we showed that a pig toilet offers the possibility to create littered lying areas, possibly increasing animal welfare.

Two macrocyclic architectures comprising oligothiophene strands that connect the imide positions of a perylene bisimide (PBI) dye have been synthesized via a platinum-mediated cross-coupling strategy. The crystal structure of the double bridged PBI reveals all syn-arranged thiophene units that completely enclose the planar PBI chromophore via a 12-membered macrocycle. The target structures were characterized by steady-state UV/Vis absorption, fluorescence and transient absorption spectroscopy, as well as cyclic and differential pulse voltammetry. Both donor-acceptor dyads show ultrafast Förster Resonance Energy Transfer and photoinduced electron transfer, thereby leading to extremely low fluorescence quantum yields even in the lowest polarity cyclohexane solvent., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Chemical doping controls the electronic properties of organic semiconductors, but so far, doping protocols and mechanisms are less developed than in conventional semiconductors. Here we describe a unique, site-specific, n-type surface doping mechanism for single crystals of two benchmark organic semiconductors that produces dramatic improvement in electron transport and provides unprecedented evidence for doping-induced space charge. The surface doping chemistry specifically targets crystallographic step edges, which are known electron traps, simultaneously passivating the traps and releasing itinerant electrons. The effect on electron transport is profound: field-effect electron mobility increases by as much as a factor of ten, and its temperature-dependent behaviour switches from thermally activated to band-like. Our findings suggest new site-specific strategies to dope organic semiconductors that differ from the conventional redox chemistry of randomly distributed substitutional impurities. Critically, they also verify the presence of doping-induced electron atmospheres, confirming long-standing expectations for organic systems from conventional solid-state theory., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

Aggregation-induced emission enhancement (AIEE) phenomena received great popularity during the last decade but in most cases insights into the packing structure - fluorescence properties remained scarce. Here, an almost non-fluorescent merocyanine dye was equipped with large solubilizing substituents, which allowed the investigation of it's aggregation behaviour in unpolar solvents over a large concentration range (10 -2 to 10 -7 M). In depth analysis of the self-assembly process by concentration-dependent UV/Vis spectroscopy at different temperatures revealed a two-step anti-cooperative aggregation mechanism. In the first step a co-facially stacked dimer is formed driven by dipole-dipole interactions. In a second step these dimers self-assemble to give an oligomer stack consisting of about ten dyes. Concentration- and temperature-dependent UV/Vis spectroscopy provided insight into the thermodynamic parameters and allowed to identify conditions where either the monomer, the dimer or the decamer prevails. The centrosymmetric dimer structure could be proven by 2D NMR spectroscopy. For the larger decamer atomic force microscopy (AFM), diffusion ordered spectroscopy (DOSY) and vapour pressure osmometric (VPO) measurements consistently indicated that it is of small and defined size. Fluorescence, circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopy provided insights into the photofunctional properties of the dye aggregates. Starting from an essentially non-fluorescent monomer ( Φ Fl = 0.23%) a strong AIEE effect with excimer-type fluorescence (large Stokes shift, increased fluorescence lifetime) is observed upon formation of the dimer ( Φ Fl = 2.3%) and decamer ( Φ Fl = 4.5%) stack. This increase in fluorescence is accompanied for both aggregates by an aggregation-induced CPL enhancement with a strong increase of the g lum from ∼0.001 for the dimer up to ∼0.011 for the higher aggregate. Analysis of the radiative and non-radiative decay rates corroborates the interpretation that the AIEE effect originates from a pronounced decrease of the non-radiative rate due to π-π-stacking induced rigidification that outmatches the effect of the reduced radiative rate that originates from the H-type exciton coupling in the co-facially stacked dyes., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A series of perylene bisimide (PBI) dyes bearing various aryl substituents in 1,6,7,12 bay positions has been synthesized by Suzuki cross-coupling reaction. These molecules exhibit an exceptionally large and conformationally fixed twist angle of the PBI π-core due to the high steric congestion imparted by the aryl substituents in bay positions. Single crystal X-ray analyses of phenyl-, naphthyl- and pyrenyl-functionalized PBIs reveal interlocked π-π-stacking motifs, leading to conformational chirality and the possibility for the isolation of enantiopure atropoisomers by semipreparative HPLC. The interlocked arrangement endows these molecules with substantial racemization barriers of about 120 kJ mol -1 for the tetraphenyl- and tetra-2-naphthyl-substituted derivatives, which is among the highest racemization barriers for axially chiral PBIs. Variable temperature NMR studies reveal the presence of a multitude of up to fourteen conformational isomers in solution that are interconverted via smaller activation barriers of about 65 kJ mol -1 . The redox and optical properties of these core-twisted PBIs have been characterized by cyclic voltammetry, UV/Vis/NIR and fluorescence spectroscopy and their respective atropo-enantiomers were further characterized by circular dichroism (CD) and circular polarized luminescence (CPL) spectroscopy., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Fluorophores emitting in the near-infrared (NIR) are highly desired for various applications, but increasing nonradiative rates cause severe fluorescence quenching for wavelengths beyond 800 nm. Here, a bis(squaraine) dye is reported that bears two NIR dyes in a head-to-tail chromophore arrangement. This arrangement leads to intra molecular J-type exciton coupling, resulting in an absorption maximum at 961 nm and a fluorescence peak at 971 nm with a quantum yield of 0.33% in chloroform. In less polar toluene, the bis(squaraine) self-assembles into nanofibers, affording another bathochromic shift with an absorption maximum at 1095 nm and a fluorescence peak at 1116 nm originating from inter molecular J-type coupling.

In the current review, we argue that experimental results usually interpreted as evidence for cognitive resource limitations could also reflect functional necessities of human information processing. First, we point out that selective processing of only specific features, objects, or locations at each moment in time allows humans to monitor the success and failure of their own overt actions and covert cognitive procedures. We then proceed to show how certain instances of selectivity are at odds with commonly assumed resource limitations. Next, we discuss examples of seemingly automatic, resource-free processing that challenge the resource view but can be easily understood from the functional perspective of monitoring cognitive procedures. Finally, we suggest that neurophysiological data supporting resource limitations might actually reflect mechanisms of how procedural control is implemented in the brain., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Ansorge, Büsel, Forstinger, Gugerell, Grüner, Pomper, Stolte, Schmid and Valuch.)

A highly sensitive short-wave infrared (SWIR, λ > 1000 nm) organic photodiode (OPD) is described based on a well-organized nanocrystalline bulk-heterojunction (BHJ) active layer composed of a dicyanovinyl-functionalized squaraine dye (SQ-H) donor material in combination with PC 61 BM. Through thermal annealing, dipolar SQ-H chromophores self-assemble in a nanoscale structure with intermolecular charge transfer mediated coupling, resulting in a redshifted and narrow absorption band at 1040 nm as well as enhanced charge carrier mobility. The optimized OPD exhibits an external quantum efficiency (EQE) of 12.3% and a full-width at half-maximum of only 85 nm (815 cm -1 ) at 1050 nm under 0 V, which is the first efficient SWIR OPD based on J-type aggregates. Photoplethysmography application for heart-rate monitoring is successfully demonstrated on flexible substrates without applying reverse bias, indicating the potential of OPDs based on short-range coupled dye aggregates for low-power operating wearable applications., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

We report the development of a new spectroscopic scheme, coherent two-dimensional (2D) electronic spectroelectrochemistry. Conventional 2D electronic spectroscopy has become well established to investigate molecular energy transfer, charge transfer, or structural dynamics with femtosecond time resolution following electronic excitation, providing frequency resolution for both the excitation and the detection step. Here we combine this method with electrochemistry in a flow cell. Thus we have established access to the dynamics of various oxidized and reduced molecular species in solution. We investigate the photophysics of a tetraphenoxy-substituted perylene bisimide dye and its reduced species as a proof of principle and find substantially different dynamics for the neutral and the twofold reduced compound. The electrochemical flow cell is furthermore applied in conventional transient absorption spectroscopy and photoluminescence spectroscopies as an application in different setups., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Visual motion captures attention, but little is known about the automaticity of these effects. Here, we tested if deviant flicker frequencies, as one form of motion, automatically capture attention. Observers searched for a vertical target among tilted distractors. Prior to the target display, a cue array of sinusoidally modulating (flickering) annuli, each surrounding one location of the subsequent target(-plus-distractors) display was presented for variable durations. Annuli either flickered all at 1 Hz (neutral condition, no-singleton cue), or a single annulus flickered at a unique frequency of 5 Hz, 10 Hz, or 15 Hz. The location of this singleton-frequency cue was uncorrelated with target location. Thus, we could measure benefits (target at cued location) and costs (target ≠ cued location) for cues of different frequencies and durations. The results showed that deviant flicker frequencies capture attention, as we observed benefits and costs, falsifying that nonspatial filtering accounted for the cueing effect. In line with automatic capture, cueing was effective in singleton (Experiment 1) and nonsingleton search tasks (Experiment 2), and is thus not dependent on ("top-down") singleton detection mode. Moreover, analysis of results ruled out trial-by-trial "swapping" of flicker frequencies from preceding target to subsequent distractor locations. Results also revealed increasing cueing effects with higher cue flicker frequency and longer duration. This indicates a significantly longer period of automatic capture by sinusoidal flicker than the typical inhibition of return observed around 250 ms after the onset of uninformative static or single-transient cues.

Linking arbitrary shapes (e.g., circles, squares, and triangles) to personal labels (e.g., self, friend, or stranger) or reward values (e.g., £18, £6, or £2) results in immediate processing benefits for those stimuli that happen to be associated with the self or high rewards in perceptual matching tasks. Here we further explored how social and reward associations interact with multisensory stimuli by pairing labels and objects with tones (low, medium, and high tones). We also investigated whether self and reward biases persist for multisensory stimuli with the label removed after an association had been made. Both high reward stimuli and those associated with the self, resulted in faster responses and improved discriminability (i.e., higher d' ), which persisted for multisensory stimuli even when the labels were removed. However, these self- and reward-biases partly depended on the specific alignment between the physical tones (low, medium, and high) and the conceptual (social or reward) order. Performance for reward associations improved when the endpoints of low or high rewards were paired with low or high tones; meanwhile, for personal associations, there was a benefit when the self was paired with either low or high tones, but there was no effect when the stranger was associated with either endpoint. These results indicate that, unlike reward, social personal associations are not represented along a continuum with two marked endpoints (i.e., self and stranger) but rather with a single reference point (the self vs. other)., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Stolte, Spence and Barutchu.)

The interactions between auxochromic groups in π-conjugated functional molecules dictate their electronic properties. From the standpoint of potential applications, understanding and control of such interactions is a vital requirement for the material design. In this communication, we describe the design, synthesis, and functional properties of a novel class of helically chiral diimide molecules, namely, [ n ]HDI-OMe ( n  = 5, 6, and 7), in which two imide units are connected via an [ n ]helicene skeleton. The experimental results supported by quantum chemical calculations reveal that the helical backbone in these molecules offers not only through-bond but also through-space conjugation between imide groups, which leads to distinct optical and electrochemical properties when compared to the related [ n ]helicenes and rylene diimides.

Attention deficit/hyperactivity disorder (ADHD) is a debilitating disorder and most research therefore focuses on its deficits and its treatment. Research on the potential positive sides of ADHD is limited, and although a comprehensive overview of empirical studies on this subject is missing, it has been suggested that ADHD is associated with enhanced creativity. To identify important relations, trends and gaps in the literature, we review 31 behavioral studies on creativity and ADHD, distinguishing different research designs, age groups, creativity measurements and effects of psychostimulants, as well as reflecting the potential underlying neural mechanisms of creativity and ADHD. Most studies find evidence for increased divergent thinking for those with high ADHD scores (subclinical) but not for those with the disorder (clinical). The rates of creative abilities/achievements were high among both clinical and subclinical groups. We found no evidence for increased convergent thinking abilities in ADHD, nor did we find an overall negative effect of psychostimulants on creativity. Neuroscientific findings suggest candidate regions as well as mechanisms that should be studied further to increase our understanding of the relationship between creativity and ADHD. We propose research opportunities to boost the knowledge needed to better understand the potential positive side of ADHD., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

A new perylene bisimide (PBI), with a fluorescence quantum yield up to unity, self-assembles into two polymorphic supramolecular polymers. This PBI bears four solubilizing acyloxy substituents at the bay positions and is unsubstituted at the imide position, thereby allowing hydrogen-bond-directed self-assembly in nonpolar solvents. The formation of the polymorphs is controlled by the cooling rate of hot monomer solutions. They show distinctive absorption profiles and morphologies and can be isolated in different polymorphic liquid-crystalline states. The interchromophoric arrangement causing the spectral features was elucidated, revealing the formation of columnar and lamellar phases, which are formed by either homo- or heterochiral self-assembly, respectively, of the atropoenantiomeric PBIs. Kinetic studies reveal a narcissistic self-sorting process upon fast cooling, and that the transformation into the heterochiral (racemic) sheetlike self-assemblies proceeds by dissociation via the monomeric state., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Histone deacetylases (HDACs) are important regulators of epigenetic gene modification that are involved in the transcriptional control of metabolism. In particular class IIa HDACs have been shown to affect hepatic gluconeogenesis and previous approaches revealed that their inhibition reduces blood glucose in type 2 diabetic mice. In the present study, we aimed to evaluate the potential of class IIa HDAC inhibition as a therapeutic opportunity for the treatment +of metabolic diseases. For that, siRNAs selectively targeting HDAC4, 5 and 7 were selected and used to achieve a combinatorial knockdown of these three class IIa HDAC isoforms. Subsequently, the hepatocellular effects as well as the impact on glucose and lipid metabolism were analyzed in vitro and in vivo . The triple knockdown resulted in a statistically significant decrease of gluconeogenic gene expression in murine and human hepatocyte cell models. A similar HDAC-induced downregulation of hepatic gluconeogenesis genes could be achieved in mice using a liver-specific lipid nanoparticle siRNA formulation. However, the efficacy on whole body glucose metabolism assessed by pyruvate-tolerance tests were only limited and did not outweigh the safety findings observed by histopathological analysis in spleen and kidney. Mechanistically, Affymetrix gene expression studies provide evidence that class IIa HDACs directly target other key factors beyond the described forkhead box (FOXP) transcription regulators, such as hepatocyte nuclear factor 4 alpha (HNF4a). Downstream of these factors several additional pathways were regulated not merely including glucose and lipid metabolism and transport. In conclusion, the liver-directed combinatorial knockdown of HDAC4, 5 and 7 by therapeutic siRNAs affected multiple pathways in vitro , leading in vivo to the downregulation of genes involved in gluconeogenesis. However, the effects on gene expression level were not paralleled by a significant reduction of gluconeogenesis in mice. Combined knockdown of HDAC isoforms was associated with severe adverse effects in vivo , challenging this approach as a treatment option for chronic metabolic disorders like type 2 diabetes., (Copyright © 2020 Ziegler, Raichur, Brunner, Hemmann, Stolte, Schwahn, Prochnow, Metz-Weidmann, Tennagels, Margerie, Wohlfart and Bielohuby.)

The one-step reaction of a dicyanovinyl-functionalized squaric acid with Fischer bases afforded C2v symmetric squaraine dyes with rigid planar structures due to intramolecular N-HO hydrogen bonds. Dense molecular packing, decrease of HOMO level, and sufficient thermal stability for sublimation enabled vacuum-processed OTFTs with hole mobility up to 0.32 cm2 V-1 s-1 and current on/off ratio of 106.

Exciton migration in self-assembled supramolecular ensembles of dye molecules is controlled by the electronic coupling between adjacent sites, the delocalization of the excitation and thereby by the packing arrangement. Here, we put emphasis on the packing structure and analyze the exciton migration in two perylene bisimide-based J-aggregates composed of almost identical molecular building blocks but forming double-strand versus quadruple-strand slip-stacked supramolecular architectures. Analyzing ultrafast transient absorption spectra in dependence on the exciton density by a kinetic model for exciton-exciton annihilation based on incoherent transfer demonstrates that the migration is quasi one-dimensional. The migration distance is enhanced by a beneficial geometrical structure. We find a factor of more than two between the diffusion lengths of 188 and 77 nm for the double- and quadruple-stranded system. The supramolecular design efficiently influences the exciton mobility and minor structural changes have a pronounced influence on functional properties of dye aggregates.

Flucloxacillin (FLU), an isoxazolyl penicillin, is widely used for the treatment of different bacterial infections in intensive care units (ICU). Being highly bound to plasma proteins, FLU is prone to drug-drug interactions (DDI) when administered concurrently with other drugs. As FLU is binding to both Sudlow's site I and site II of human serum albumin (HSA), competitive and allosteric interactions with other drugs, highly bound to the same sites, seem conceivable. Knowledge about interaction(s) of FLU with the widely used anticancer agents paclitaxel (PAC), imatinib (IMA), and 5-fluorouracil (5-FU is scarce. The effects of the selected anticancer agents on the unbound fraction of FLU were evaluated in pooled plasma as well as in HSA and α-1-acid glycoprotein (AGP) samples, the second major drug carrier in plasma. FLU levels in spiked samples were analyzed by LC-MS/MS after ultrafiltration. Significant increase in FLU unbound fraction was observed when in combination with PAC and IMA and to a lesser extent with 5-FU. Furthermore, significant binding of FLU to AGP was observed. Collectively, this is the first study showing the binding of FLU to AGP as well as demonstrating a significant DDI between PAC/IMA/5-FU and FLU., Competing Interests: The authors declare no conflict of interest.

Continuously tracking cognitive demands via pupil dilation is a desirable goal for the monitoring and investigation of cognitive performance in applied settings where the exact time point of mental engagement in a task is often unknown. Yet, hitherto no experimentally validated algorithm exists for continuously estimating cognitive demands based on pupil size. Here, we evaluated the performance of a continuously operating algorithm that is agnostic of the onset of the stimuli and derives them by way of retrospectively modeling attentional pulses (i.e., onsets of processing). We compared the performance of this algorithm to a standard analysis of stimulus-locked pupil data. The pupil data were obtained while participants performed visual search (VS) and visual working memory (VWM) tasks with varying cognitive demands. In Experiment 1, VS was performed during the retention interval of the VWM task to assess interactive effects between search and memory load on pupil dilation. In Experiment 2, the tasks were performed separately. The results of the stimulus-locked pupil data demonstrated reliable increases in pupil dilation due to high VWM load. VS difficulty only affected pupil dilation when simultaneous memory demands were low. In the single task condition, increased VS difficulty resulted in increased pupil dilation. Importantly, online modeling of pupil responses was successful on three points. First, there was good correspondence between the modeled and stimulus locked pupil dilations. Second, stimulus onsets could be approximated from the derived attentional pulses to a reasonable extent. Third, cognitive demands could be classified above chance level from the modeled pupil traces in both tasks.

The goal of the current study was to investigate the role of executive functions in mathematical creativity. The sample included 278 primary school children (ages 8-13). Two models were compared: the starting model tested whether executive functions (shifting, updating, and inhibition), domain-general creativity, and mathematical ability directly predicted mathematical creativity. The second model, which fitted the data best, included the additional assumption that updating influences mathematical creativity indirectly through mathematical ability and domain-general creativity. Updating was positively related to mathematical creativity. Additionally, updating was positively related to mathematical ability and domain-general creativity. Inhibition, shifting, domain-general creativity and mathematical ability did not have a significant contribution to either model but did positively correlate with mathematical creativity. This study reports the first empirical evidence that updating is a predictor of mathematical creativity in primary school children and demonstrates that creativity is a higher order cognitive process, activating a variety of cognitive abilities.

In their seminal paper 'Is our self nothing but reward', Northoff and Hayes (Biol Psychiatry 69(11):1019-1025, Northoff, Hayes, Biological Psychiatry 69(11):1019-1025, 2011) proposed three models of the relationship between self and reward and opened a continuing debate about how these different fields can be linked. To date, none of the proposed models received strong empirical support. The present study tested common and distinct effects of personal relevance and reward values by de-componenting different stages of perceptual decision making using a drift-diffusion approach. We employed a recently developed associative matching paradigm where participants (N = 40) formed mental associations between five geometric shapes and five labels referring personal relevance in the personal task, or five shape-label pairings with different reward values in the reward task and then performed a matching task by indicating whether a displayed shape-label pairing was correct or incorrect. We found that common effects of personal relevance and monetary reward were manifested in the facilitation of behavioural performance for high personal relevance and high reward value as socially important signals. The differential effects between personal and monetary relevance reflected non-decisional time in a perceptual decision process, and task-specific prioritization of stimuli. Our findings support the parallel processing model (Northoff & Hayes, Biol Psychiatry 69(11):1019-1025, Northoff, Hayes, Biological Psychiatry 69(11):1019-1025, 2011) and suggest that self-specific processing occurs in parallel with high reward processing. Limitations and further directions are discussed.

Fluorophores with high quantum yields are desired for a variety of applications. Optimization of promising chromophores requires an understanding of the non-radiative decay channels that compete with the emission of photons. We synthesized a new derivative of the famous laser dye 4-dicyanomethylen-2-methyl-6- p -dimethylaminostyryl-4 H -pyran ( DCM ), i.e. , merocyanine 4-(dicyanomethylene)-2- tert -butyl-6-[3-(3-butyl-benzothiazol-2-ylidene)1-propenyl]-4 H -pyran ( DCBT ). We measured fluorescence lifetimes and quantum yields in a variety of solvents and found a trend opposite to the energy gap law. This motivated a theoretical investigation into the possible non-radiative decay channels. We propose that a barrier to a conical intersection exists that is very sensitive to the solvent polarity. The conical intersection is characterized by a twisted geometry which allows a subsequent photoisomerization. Transient absorption measurements confirmed the formation of a photoisomer in unpolar solvents, while the measurements of fluorescence quantum yields at low temperature demonstrated the existence of an activation energy barrier., (This journal is © The Royal Society of Chemistry 2019.)

The self-assembly of a bowl-shaped naphthalimide-annulated corannulene of high solubility has been studied in a variety of solvents by NMR and UV/Vis spectroscopy. Evaluation by the anti-cooperative K 2 - K  M 6  M -1 in methylcyclohexane, which is comparable to the association constants given for planar phthalocyanine and perylene bisimide dyes., Competing Interests: The authors declare no conflict of interest., (©2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Strongly emissive solid-state materials are mandatory components for many emerging optoelectronic technologies, but fluorescence is often quenched in the solid state owing to strong intermolecular interactions. The design of new organic pigments, which retain their optical properties despite their high tendency to crystallize, could overcome such limitations. Herein, we show a new material with monomer-like absorption and emission profiles as well as fluorescence quantum yields over 90 % in its crystalline solid state. The material was synthesized by attaching two bulky tris(4-tert-butylphenyl)phenoxy substituents at the perylene bisimide bay positions. These substituents direct a packing arrangement with full enwrapping of the chromophore and unidirectional chromophore alignment within the crystal lattice to afford optical properties that resemble those of their natural pigment counterparts, in which chromophores are rigidly embedded in protein environments., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

A novel core-shell structured columnar liquid crystal composed of a donor-acceptor dyad of tetraphenoxy perylene bisimide (PBI), decorated with four bithiophene units on the periphery, was synthesized. This molecule self-assembles in solution into helical J-aggregates guided by π-π interactions and hydrogen bonds which organize into a liquid-crystalline (LC) columnar hexagonal domain in the solid state. Donor and acceptor moieties exhibit contrasting exciton coupling behavior with the PBIs' (J-type) transition dipole moment parallel and the bithiophene side arms' (H-type) perpendicular to the columnar axis. The dyad shows efficient energy and electron transfer in solution as well as in the solid state. The synergy of photoinduced electron transfer (PET) and charge transport along the narcissistically self-assembled core-shell structure enables the implementation of the dye in two-contact photoconductivity devices giving rise to a 20-fold increased photoresponse compared to a reference dye without bithiophene donor moieties., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Boron-doping has long been recognized as a promising LUMO energy-lowering modification of graphene and related polycyclic aromatic hydrocarbons (PAHs). Unfortunately, synthetic difficulties have been a significant bottleneck for the understanding, optimization, and application of precisely boron-doped PAHs for optoelectronic purposes. Herein, a facile one-pot hydroboration electrophilic borylation cascade/dehydrogenation approach from simple alkene precursors is coupled with postsynthetic B-substitution to give access to ten ambient-stable core- and periphery-tuned boron-doped PAHs. These include large hitherto unknown doubly boron-doped analogues of anthanthrene and triangulene. Crystallographic, optical, electrochemical, and computational studies were performed to clarify the effect of boron-doped PAH shape, size, and structure on optoelectronic properties. Our molecular tuning allowed the synthesis of molecules exhibiting visible-range absorption, near-unity fluorescence quantum yields, and, to our knowledge, the most facile electrochemical reductions of any reported ambient-stable boron-doped PAHs (corresponding to LUMO energy levels as low as fullerenes). Finally, our study describes the first implementation of a precise three-coordinate boron-substituted PAH as an acceptor material in organic solar cells with power conversion efficiencies (PCEs) of up to 3%.