Skeletal Editing—Nitrogen Deletion of Secondary Amines by Anomeric Amide Reagents

Late-stage modification is highly desirable for the diversification and modification of biologically active compounds. Peripheral editing (e.g., C−H activation) has been the predominant methodology, whereas skeletal editing is in its infancy. The single-atom N-deletion using anomeric amide reagents constitutes a powerful tool to modify the underlying molecular skeletons of secondary amines. N-pivaloyloxy-N-alkoxyamide is easily prepared on a large scale and promotes C−C bond formation in good yields under the extrusion of N2 for a variety of (cyclic) aliphatic amines. The exploitation of widely available amines allows the use of existing amine synthesis protocols to translate into the construction of new C−C bonds, enabling ring contraction and the potential for structure optimization of biologically active compounds

A Brief History of OLEDs—Emitter Development and Industry Milestones

Organic light‐emitting diodes (OLEDs) have come a long way ever since their first introduction in 1987 at Eastman Kodak. Today, OLEDs are especially valued in the display and lighting industry for their promising features. As one of the research fields that equally inspires and drives development in academia and industry, OLED device technology has continuously evolved over more than 30 years. OLED devices have come forward based on three generations of emitter materials relying on fluorescence (first generation), phosphorescence (second generation), and thermally activated delayed fluorescence (third generation). Furthermore, research in academia and industry toward the fourth generation of OLEDs is in progress. Excerpts from the history of green, orange‐red, and blue OLED emitter development on the side of academia and milestones achieved by key players in the industry are included in this report

[2.2]Paracyclophane-substituted chiral multiresonant thermally activated delayed fluorescence emitters for efficient organic light-emitting diodes

The authors aregrateful to the EPSRC for financial support (grant EP/W0151371/1and EP/W007517/1). Y.X. thanks the China Scholarship Council(202106310038) for support. J.S. thanks the Jürgen Manchot Foundation, the Karlsruhe School of Optics and Photonics, and Dr. Erik Strandberg and Bianca Posselt, for their help in ECD measurements.The authors thank the European Commission Research ExecutiveAgency (Grant Agreement number: 101073045−TADFsolutions−HORIZON-MSCA-2021-DN) and the EPSRC (EP/X026175/1) for financial support. The authors acknowledge the Ministère de l’EnseignementSupérieur et de la Recherche and the Centre National de la RechercheScientifique (CNRS).The study reports two pairs of chiral multi-resonant thermally activated delayed fluorescence (MR-TADF) materials PCP-DiKTa and Czp-DiKTa by decorating a known MR-TADF core, DiKTa, with different [2.2]paracyclophane (PCP) based planar chiral groups. PCP-DiKTa shows narrow sky-blue emission with a full width at half maximum (FWHM) of 44 nm, while the emission of Czp-DiKTa is slightly broader with a FWHM of 66 nm and redshifted. Both emitters show high photoluminescence quantum yields of 93 and 99% for PCP-DiKTa and Czp-DiKTa, respectively. Enantiomerically pure samples of both compounds show chiroptical properties in the ground state while only Czp-DiKTa exhibits chiroptical activity in the excited state, with dissymmetry factors (|gPL|) of 4 × 10−4. Organic light-emitting diodes (OLEDs) with PCP-DiKTa and Czp-DiKTa show maximum external quantum efficiencies (EQEmax) of 25.7 and 29.2%, with λEL of 489 and 518 nm, and FWHMs of 53 and 69 nm, respectively. These EQEmax values are higher than those of other reported devices employing PCP-based D-A type emitters. This work demonstrates that the PCP moiety is not only a powerful building block to develop planar chiral emitters but one that is compatible with the fabrication of high efficiency devices.Peer reviewe

A novel carbazolophane : a comparison of the performance of two planar chiral CP-TADF emitters

Jürgen Manchot Foundation Deutsche Forschungsgemeinschaft. Grant Number: EXC-2082/1–390761711 China Scholarship Council. Grant Number: 202106310038 Engineering and Physical Sciences Research Council. Grant Numbers: EP/R035164/1, EP/W015137/1, EP/W524505/1 Helmholtz Association Program Ministère de l’Enseignement Supérieur et de la Recherche Centre National de la Recherche ScientifiqueThe prototypical example of a (cyclo)phane, [2.2]paracyclophane (PCP), has proven to be a versatile stereogenic moiety within the design of circularly polarized thermally activated delayed fluorescence (CP-TADF) emitters; however, the exploration of other cyclophanes within CP-TADF emitter design has been largely neglected. Here, a comparative study of the photophysical and optoelectronic properties of two cyclophane emitters, (1,7)tBuCzpPhTrz and its isomer (1,4)tBuCzpPhTrz, is presented. The carbazolophane-triazine compound (1,7)tBuCzpPhTrz, obtained via an unprecedented intramolecular rearrangement, is the first example of a planar chiral TADF emitter deviating from the PCP scaffold. Significant geometrical change of the enclosed carbazole in (1,7)tBuCzp results in an attenuation of the donor strength, while the merits of rigidity and steric bulk remain. In particular, the full width at half maximum (FWHM) of the photoluminescence spectrum in toluene of (1,7)tBuCzpPhTrz is reduced by 34% and blue-shifted by 20 nm compared to that of (1,4)tBuCzpPhTrz. In doped films, the compounds reach high photoluminescence quantum yields (ΦPL) of 91 and 81%, respectively. The chiroptical properties reveal dissymmetry factors |gPL| of up to 5 ? 10?4. These results demonstrate the impact of the cyclophane for the development of CP-TADF materials and add to the currently limited scope of available planar chiral donors.Peer reviewe

Risk of post-acute sequelae of SARS-CoV-2 infection associated with pre-coronavirus disease obstructive sleep apnea diagnoses: an electronic health record-based analysis from the RECOVER initiative

Obstructive sleep apnea (OSA) has been associated with more severe acute coronavirus disease-2019 (COVID-19) outcomes. We assessed OSA as a potential risk factor for Post-Acute Sequelae of SARS-CoV-2 (PASC).We assessed the impact of preexisting OSA on the risk for probable PASC in adults and children using electronic health record data from multiple research networks. Three research networks within the REsearching COVID to Enhance Recovery initiative (PCORnet Adult, PCORnet Pediatric, and the National COVID Cohort Collaborative [N3C]) employed a harmonized analytic approach to examine the risk of probable PASC in COVID-19-positive patients with and without a diagnosis of OSA prior to pandemic onset. Unadjusted odds ratios (ORs) were calculated as well as ORs adjusted for age group, sex, race/ethnicity, hospitalization status, obesity, and preexisting comorbidities.Across networks, the unadjusted OR for probable PASC associated with a preexisting OSA diagnosis in adults and children ranged from 1.41 to 3.93. Adjusted analyses found an attenuated association that remained significant among adults only. Multiple sensitivity analyses with expanded inclusion criteria and covariates yielded results consistent with the primary analysis.Adults with preexisting OSA were found to have significantly elevated odds of probable PASC. This finding was consistent across data sources, approaches for identifying COVID-19-positive patients, and definitions of PASC. Patients with OSA may be at elevated risk for PASC after SARS-CoV-2 infection and should be monitored for post-acute sequelae

Systematic review of tools to measure outcomes for young children with autism spectrum disorder

Background: The needs of children with autism spectrum disorder (ASD) are complex and this is reflected in the number and diversity of outcomes assessed and measurement tools used to collect evidence about children's progress. Relevant outcomes include improvement in core ASD impairments, such as communication, social awareness, sensory sensitivities and repetitiveness, skills such as social functioning and play, participation outcomes such as social inclusion, and parent and family impact. Objectives: To examine the measurement properties of tools used to measure progress and outcomes in children with ASD up to the age of 6 years. To identify outcome areas regarded as important by people with ASD and parents. Methods: The MeASURe (Measurement in Autism Spectrum disorder Under Review) research collaboration included ASD experts and review methodologists. We undertook systematic review of tools used in ASD early intervention and observational studies from 1992 to 2013, systematic review, using the COSMIN checklist (Consensus-based Standards for the selection of health Measurement Instruments) of papers addressing the measurement properties of identified tools in children with ASD, and synthesis of evidence and gaps. The review design and process was informed throughout by consultation with stakeholders including parents, young people with ASD, clinicians and researchers. Results: The conceptual framework developed for the review was drawn from the International Classification of Functioning, Disability and Health, including the domains 'Impairments', 'Activity Level Indicators', 'Participation', and 'Family Measures'. In review 1, 10,154 papers were sifted - 3091 by full text - and data extracted from 184, in total, 131 tools were identified, excluding observational coding, study-specific measures and those not in English. In review 2, 2665 papers were sifted and data concerning measurement properties of 57 (43%) tools were extracted from 128 papers. Evidence for the measurement properties of the reviewed tools was combined with information about their accessibility and presentation. Twelve tools were identified as having the strongest supporting evidence, the majority measuring autism characteristics and problem behaviour. The patchy evidence and limited scope of outcomes measured mean these tools do not constitute a 'recommended battery' for use. In particular,there is little evidence that the identified tools would be good at detecting change in intervention studies. The obvious gaps in available outcome measurement include well-being and participation outcomes for children, and family quality-of-life outcomes, domains particularly valued by our informants (young people with ASD and parents). Conclusions: This is the first systematic review of the quality and appropriateness of tools designed to monitor progress and outcomes of young children with ASD. Although it was not possible to recommend fully robust tools at this stage, the review consolidates what is known about the field and will act as a benchmark for future developments. With input from parents and other stakeholders, recommendations are made about priority targets for research. Future work: Priorities include development of a tool to measure child quality of life in ASD, and validation of a potential primary outcome tool for trials of early social communication intervention. Study registration: This study is registered as PROSPERO CRD42012002223. Funding: The National Institute for Health Research Health Technology Assessment programme

Molecular Structuring of Novel Chiral Polymers via Cyclophane-based Monomer Design Strategies

Structuring soft matter with precise control over molecular arrangements, nanoscale morphologies, especially aiming at functional polymers featuring chirality or helicity, responsiveness, and other features, has been a great research objective, which yet remains a challenging task. In this research work, we developed new design strategies for molecular structuring of an entirely new class of chiral polymers based on [2.2]paracyclophane derivatives. The grafting of tunable functional moieties onto [2.2]paracyclophane enables post-polymerization modification, where diverse perspective applications can be envisioned. In particular, chiral vinyl[2.2]paracyclophane and [2.2]paracyclophane-substituted diazoacetate give novel poly[2.2]paracyclophanylethenes and poly[2.2]paracyclophanylmethenes, respectively

Carbazolophane Enhances the Efficiency of Thermally Activated Delayed Fluorescence in Carbene Coinage Metal Amides

Carbene coinage metal carbazolates are currently the most efficient organometallic TADF emitters. Herein we report on the photophysical influence of introducing a [2.2]paracyclophane moiety via a carbazolophane ligand instead of carbazolate, which greatly enhances the radiative rate constants by a factor of three to 1-3·106 s-1 for triplet exciton emission