Synthesis of a new polyfluorinated vinylogue of tetrathiafulvalene through 1,3-dipolar cycloaddition of ethyl beta-bromoperfluorodithiocrotonate with dimethyl acetylenedicarboxylate

The ethyl ester of beta-bromoperfluorodithiocrotonic acid reacts with dimethyl acetylenedicarboxylate to give 1,4-difluoro-2,3-bis(trifluoromethyl)-but-2-ene-1,4-diylidene-2,2'-bis(4',5'-dicarbomethoxy-1',3'-dithiole) (4), a new type of vinylogue of tetrathiafulvalene. The thermal transformations of this compound lead, depending on the temperature, to the formation of the cyclization products: 11,14-difluoro-2,3,8,9-tetra(carbomethoxy)-12,13-bis(trifluoromethyl)-1,4,7,10-tetrathiadispiro[4.0.4.4]tetradeca-2,8,11,13-tetraene (8) or 5,8-difluoro-6,7-bis(trifluoromethyl)-2,3-bis(carboxymethyl)-1,4-benzodithiine (11).     

Intramolecular Cyclizations of Allenic Acylureas and -Amides

Allenic acids are found to add to dicyclohexylcarbodiimide affording, in the presence of Et₂NH, the 4H-1,3-oxazin-4-ones 5 via 4 . Under neutral conditions, they add to diaryl- or pyridyl(cyclohexyl)carbodiimides and triphenylketene imine to give the corresponding tricyclo[5.2.2.0^1,5]undeca-4,8,10-trien-3-ones 7 , 8 , 9 , and 12 . The allenic phenyl ester 13a dimerises, on heating in a [2+2] head-to-head fashion, to 14 but fails to undergo intramolecular Diels-Alder cyclization, to 15 .     

Combining Deep Eutectic Solvents with TEMPO-based Polymer Electrodes: Influence of Molar Ratio on Electrode Performance**

For sustainable energy storage, all-organic batteries based on redox-active polymers promise to become an alternative to lithium ion batteries. Yet, polymers contribute to the goal of an all-organic cell as electrodes or as solid electrolytes. Here, we replace the electrolyte with a deep eutectic solvent (DES) composed of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) and N-methylacetamide (NMA), while using poly(2,2,6,6-tetramethylpiperidin-1-yl-oxyl methacrylate) (PTMA) as cathode. The successful combination of a DES with a polymer electrode is reported here for the first time. The electrochemical stability of PTMA electrodes in the DES at the eutectic molar ratio of 1 : 6 is comparable to conventional battery electrolytes. More viscous electrolytes with higher salt concentration can hinder cycling at high rates. Lower salt concentration leads to decreasing capacities and faster decomposition. The eutectic mixture of 1 : 6 is best suited uniting high stability and moderate viscosity.     

Spectral Photoluminescent Parameters of Barley Seeds (Hordéum vulgáre) Infected with Fusarium ssp

We needed effective and sustainable technologies for better microbiological control of crops, including Fusarium. However, photoluminescent UV–Vis methods are potential for diagnosing plant diseases with Fusarium. It has not been sufficiently studied despite the application of these methods for other biological researches. The excitation spectrum of the seeds during infection shifts to the shorter wavelength and a new maximum appears in the region λ ≈ 232 nm. The photoluminescence of infected seeds increases with excitation by radiation of wavelengths λ_e,1 = 232 nm, λ_e,2 = 362 nm and λ_e,3 = 424 nm by 1.33–3.14 times, and λ_e,3 = 424 nm—decreases by 1.1 times. Statistical moments μ₃ and μ₄, asymmetry and kurtosis change only with short-wave excitation. When analyzing the decomposition of the frequency spectrum into Gaussian curves, the most informative ratio is the ratio of right-handed and left-handed Gaussians under excitation λ_e,2 = 362 nm and λ_e,3 = 424 nm. The ratios of their maxima change during infection by 1.36–3.2 times, and for excitation by radiation λ_e,2, the frequency boundaries of Gaussians change. The results of measurements and calculations provide a basis for the development of a method and device for photoluminescence diagnostics of fusarium seeds in UV–Vis ranges.     

Synthesis of 1,3-Dioxan-2-ones by Photo-Aerobic Selenium-π-Acid Multicatalysis

An expedient method for the synthesis of cyclic carbonates from homoallylic carbonic acid esters by means of photo-aerobic selenium-π-acid multicatalysis is reported. Until now, conceptually related methods commonly relied either on the stoichiometric addition of electrophiles onto the substrate's alkene moiety or the presence of pre-installed leaving groups in allylic position of said alkene to – in part, catalytically – initiate an intramolecular attack by an adjacent carbonic acid ester group. In sharp contrast, the current study shows that the C−C double bond of homoallylic carbonic acid esters can be directly activated by the catalytic interplay of a pyrylium dye and a diselane using ambient air as the sole oxidant and visible light as an energy source.     

Spectroscopy vs. Electrochemistry: Catalyst Layer Thickness Effects on Operando/In Situ Measurements

In recent years, operando/in situ X-ray absorption spectroscopy (XAS) has become an important tool in the electrocatalysis community. However, the high catalyst loadings often required to acquire XA-spectra with a satisfactory signal-to-noise ratio frequently imply the use of thick catalyst layers (CLs) with large ion- and mass-transport limitations. To shed light on the impact of this variable on the spectro-electrochemical results, in this study we investigate Pd-hydride formation in carbon-supported Pd-nanoparticles (Pd/C) and an unsupported Pd-aerogel with similar Pd surface areas but drastically different morphologies and electrode packing densities. Our in situ XAS and rotating disk electrode (RDE) measurements with different loadings unveil that the CL-thickness largely determines the hydride formation trends inferred from spectro-electrochemical experiments, therewith calling for the minimization of the CL-thickness in such experiments and the use of complementary thin-film control measurements.     

Synthesis and Reactivity of a Cyclooctatetraene-Like Polyphosphorus Ligand Complex [Cyclo-P8]

The thermolysis of Cp′′′Ta(CO)₄ with white phosphorus (P₄) gives access to [{Cp′′′Ta}₂(μ,η^{2 : 2 : 2 : 2 : 1 : 1}-P₈)] ( A ), representing the first complex containing a cyclooctatetraene-like (COT) cyclo-P₈ ligand. While ring sizes of n >6 have remained elusive for cyclo-P_n structural motifs, the choice of the transition metal, co-ligand and reaction conditions allowed the isolation of A . Reactivity investigations reveal its versatile coordination behaviour as well as its redox properties. Oxidation leads to dimerization to afford [{Cp′′′Ta}₄(μ₄,η^{2 : 2 : 2 : 2 : 2 : 2 : 2 : 2 : 1 : 1 : 1 : 1}-P₁₆)][TEF]₂ ( 4 , TEF=[Al(OC{CF₃}₃)₄]⁻). Reduction, however, leads to the fission of one P−P bond in A followed by rapid dimerization to form [K@[2.2.2]cryptand]₂[{Cp′′′Ta}₄(μ₄,η^{2 : 2 : 2 : 2 : 2 : 2 : 2 : 2 : 1 : 1 : 1 : 1}-P₁₆)] ( 5 ), which features an unprecedented chain-type P₁₆ ligand. Lastly, A serves as a P₂ synthon, via ring contraction to the triple-decker complex [{Cp′′′Ta}₂(μ,η^{6 : 6}-P₆)] ( B ).     

Upcycling of Polybutadiene Facilitated by Selenium-Mediated Allylic Amination

Accumulation of end-of-life plastics presents ongoing environmental concerns. One strategy to solve this grand challenge is to invent new techniques that modify post-consumer waste and impart new functionality. While promising approaches for the chemical upcycling of commodity polyolefins and polyaromatics exist, analogous approaches to repurpose unsaturated polymers (e.g., polybutadiene) are scarce. In this work, we propose a method to upcycle polybutadiene, one of the most widely used commercial rubbers, via a mild, metal-free allylic amination reaction. The resulting materials have tunable thermal and surface wetting properties as a function of both sulfonamide identity and grafting density. Importantly, this approach maintains the parent alkene microstructure without evidence of olefin reduction, olefin transposition, and/or chain scission. Based on these findings, we anticipate future applications in the remediation of complex elastomers and vulcanized rubbers.     

Differentiating between Acidic and Basic Surface Hydroxyls on Metal Oxides by Fluoride Substitution: A Case Study on Blue TiO2 from Laser Defect Engineering

Both oxygen vacancies and surface hydroxyls play a crucial role in catalysis. Yet, their relationship is not often explored. Herein, we prepare two series of TiO₂ (rutile and P25) with increasing oxygen deficiency and Ti³⁺ concentration by pulsed laser defect engineering in liquid (PUDEL), and selectively quantify the acidic and basic surface OH by fluoride substitution. As indicated by EPR spectroscopy, the laser-generated Ti³⁺ exist near the surface of rutile, but appear to be deeper in the bulk for P25. Fluoride substitution shows that extra acidic bridging OH are selectively created on rutile, while the surface OH density remains constant for P25. These observations suggest near-surface Ti³⁺ are highly related to surface bridging OH, presumably the former increasing the electron density of the bridging oxygen to form more of the latter. We anticipate that fluoride substitution will enable better characterization of surface OH and its correlation with defects in metal oxides.     

The Highly Controlled and Efficient Polymerization of Ethylene

The highly controlled and efficient polymerization of ethylene is a very attractive but challenging target. Herein we report on a Coordinative Chain Transfer Polymerization catalyst, which combines a high degree of control and very high activity in ethylene oligo- or polymerization with extremely high chain transfer agent (triethylaluminum) to catalyst ratios (catalyst economy). Our Zr catalyst is long living and temperature stable. The chain length of the polyethylene products increases over time under constant ethylene feed or until a certain volume of ethylene is completely consumed to reach the expected molecular weight. Very high activities are observed if the catalyst elongates 60 000 or more alkyl chains and the polydispersity of the strictly linear polyethylene materials obtained are very low. The key for the combination of high control and efficiency seems to be a catalyst stabilized by only one strongly bound monoanionic N-ligand.