Diels-Alder Reactivity of Triisopropylsilyl Ethynyl Substituted Acenes.

We investigated the Diels-Alder reaction of 6,13-bis(triisopropylsilylethynyl)pentacene (1) with small dienophiles such as (bridged) dihydronaphthalenes/cyclohexenes that yielded adducts at the central ring, the other dienophiles predominantly or exclusively attacked the unsubstituted off-center ring. The difference in regioselectivity was investigated by DFT calculations. Apart from dispersion interactions, it is due to the steric demand of the dienophiles, which need to fit in between the silylethynyl substituents to react at the central ring.

Stabilizing Azaheptacenes.

The symmetrical 7,16-diaza-6,8,15,17-tetrakis(triisopropylsilylethynyl)heptacene was obtained by a Pd-catalyzed reaction of a 2,3-diamino-1,4-diethynylanthracene with a 2,3-dibromo-1,4-diethynyl anthracene. Positioning the TIPS-ethynyl groups adjacent to the central ring suppresses dimerization via [4+4] cycloadditions and Diels-Alder reactions; the middle pyrazine ring renders this species stable to oxidation. A single crystal structure was obtained, and thin film transistors with μ = 0.

The Radical Anion and Dianion of Benzo[3,4]cyclobuta[1,2-]phenazine.

We present the reduction of two azaacenes (a benzo-[3,4]cyclobuta[1,2-]phenazine and a benzo[3,4]cyclobuta[1,2-]naphtho[2,3-]phenazine derivative), featuring a single cyclobutadiene unit, to their radical anions and dianions. The reduced species were produced using potassium naphthalenide in the presence of 18-crown-6 in THF. Crystal structures of the reduced representatives were obtained and their optoelectronic properties evaluated.

Efficient simulation strategy to design a safer motorcycle.

This work presents models and simulations of a numerical strategy for a time and cost-efficient virtual product development of a novel passive safety restraint concept for motorcycles. It combines multiple individual development tasks in an aggregated procedure. The strategy consists of three successive virtual development stages with a continuously increasing level of detail and expected fidelity in multibody and finite element simulation environments.

Azaarenes: 13 Rings in a Row by Cyclopentannulation.

Cyclopentannulation was explored as a strategy to access large, stable azaarenes. Buchwald-Hartwig coupling of previously reported di- and tetrabrominated cyclopentannulated N,N'-dihydrotetraazapentacenes furnished stable azaarenes with up to 13 six-membered rings in a row and a length of 3.1 nm.

Substituted Cyclopentannulated Tetraazapentacenes.

Brominated pentannulated dihydrotetraazapentacenes were prepared by gold- or palladium-catalyzed 5-endo-dig cyclization of TIPS-ethynylated dihydrotetraazaacenes (TIPS = triisopropylsilyl). Post-functionalization was demonstrated by Sonogashira alkynylation and Rosenmund-von Braun cyanation. Calculations predict these species to act as n-type semiconductors, which was verified for two derivates through characterization in organic field-effect transistors.

N-Acenoacenes: Synthesis and Solid-State Properties.

Four N-acenoacenes were synthesized and analyzed for their optoelectronic properties and solid-state packings. Two of the regioisomeric acridinoacridines are TIPS-ethynylated, whereas the other pair are Boc- and triflate substituted derivatives. The two TIPS-ethynyldiazaacenoacenes were processed into organic thin-film transistors with saturation hole mobilities reaching 2.

A Stable Hexaazaoctacene Cruciform σ-Dimer.

Buchwald-Hartwig coupling of a triisopropylsilyl (TIPS)-ethynylated dibromo-N,N'-dihydrotetraazapentacene with 1,4-bis(TIPS-ethynyl)-2,3-diaminonaphthalene furnishes a dihydrohexaazaoctacene. Its oxidation with MnO results in a 7,7'-bi(hexaazaoctacenyl). In addition to eight TIPS-ethynyl groups, the bioctacene motif protects the azaoctacene subunits.

Persistent Ambipolar Heptacenes and Their Redox Species.

Sixfold TIPS-ethynylation combined with fourfold bromination of the armchair edges furnishes a long-lived, soluble heptacene; π-extension via Stille coupling accesses a persistent tetrabenzononacene. Both types of acenes were stabilized best by double TIPS-ethynylation on every other benzene ring. Tetrabromoheptacene is an ambipolar transistor material (up to 0.

Cyclopentannulated Dihydrotetraazapentacenes.

The transition-metal-catalyzed cyclization of bissilylethynylated N,N'-dihydrotetraazapentacene (TIPS-TAP-H ) into bissilylated cyclopenta[fg,qr]pentacenes is reported. Depending on the catalyst either none, one or two silyl groups migrate and change their positions in the formed five-membered rings. The optoelectronic properties are quite similar, whereas the packing motifs differ dramatically.

Cyclodimers and Cyclotrimers of 2,3 -Bisalkynylated Anthracenes, Phenazines and Diazatetracenes.

The synthesis of novel (N-)acene-based cyclooligomers is reported. Glaser-Hay coupling of the bisethynylated monomers results in cyclodimers and cyclotrimers that are separable by column and gel-permeation chromatographies. For the diazatetracene, the use of sec-butyl-silylethynyl groups is necessary to achieve solubility.

TIPS-Ethynylated Naphthodiquinoline and Naphthodiacridine: Novel Diazabisacenes.

The synthesis of two diazabisacenes is reported. A bisboronated naphthalene was Suzuki-coupled to substituted ethyl nicotinates, then cyclized by intramolecular Friedel-Crafts acylation. The resulting diketones were alkynylated and reduced to give the title compounds, bis(TIPS-ethynyl)-substituted naphtha[1,8-gh:5,4-g'h']diquinoline and naphtho[1,8-bc:5,4-b'c']diacridine.

Evaluation of World Health Organization-Recommended Hand Hygiene Formulations.

As a result of the coronavirus disease pandemic, commercial hand hygiene products have become scarce and World Health Organization (WHO) alcohol-based hand rub formulations containing ethanol or isopropanol are being produced for hospitals worldwide. Neither WHO formulation meets European Norm 12791, the basis for approval as a surgical hand preparation, nor satisfies European Norm 1500, the basis for approval as a hygienic hand rub. We evaluated the efficacy of modified formulations with alcohol concentrations in mass instead of volume percentage and glycerol concentrations of 0.

Linear and Star-Shaped Extended Di- and Tristyrylbenzenes: Synthesis, Characterization and Optical Response to Acid and Metal Ions.

Two linear 1,4-distyrylbenzenes and five star-shaped 1,3,5-tristyrylbenzene derivatives (L and L , Y -Y and Y ) were synthesized and spectroscopically characterized. The photophysical properties, optical response to acid and metal ions were investigated. Upon backbone extension of linear distyrylbenzenes or the introduction of dibutylanilines, the electronic spectra are redshifted.

Tetrabenzononacene: "Butterfly Wings" Stabilize the Core.

In combination with bulky substituents at the core, fourfold benzannulation at the cata-positions stabilizes a nonacene sufficiently to allow its isolation and characterization by H NMR and X-ray analysis. The four benzo units blueshift the absorption spectrum in comparison to a solely linear nonacene, but significantly increase the stability in the solid state.

Effect of drinking on adiponectin in healthy men and women: a randomized intervention study of water, ethanol, red wine, and beer with or without alcohol.

Objective: Moderate alcohol consumption is associated with reduced incidence of type 2 diabetes and cardiovascular mortality and increases adiponectin concentrations, but effects might differ according to sex and beverage consumed.

Research Design And Methods: A total of 72 healthy individuals (22-56 years) were enrolled in this randomized controlled crossover trial. After washout, two interventions for 3 weeks followed: ethanol (concentration 12.