Azolium/Hydroquinone Organo-Radical Co-Catalysis: Aerobic C−C-Bond Cleavage in Ketones

Organo-radical catalysts have recently attracted great interest, and the development of this field can be expected to broaden the applications of organocatalysis. Herein, the first example of a radical-generating system is reported that does not require any photoirradiation, radical initiators, or preactivated substrates. The oxidative C−C-bond cleavage of 2-substituted cyclohexanones was achieved using an azolium salt and a hydroquinone as co-catalysts. A catalytic mechanism was proposed based on the results of diffusion-ordered spectroscopy and cyclic voltammetry measurements, as well as computational studies.     

Organometallic Molecular Wires with Thioacetylene Backbones,trans-{RS-(C≡C)n}2Ru(phosphine)4: High Conductance through Non-Aromatic Bridging Linkers

In this work, the design, synthesis, and single-molecule conductance of ethynyl- and butadiynyl-ruthenium molecular wires with thioether anchor groups [RS=n-C₆H₁₃S, p-tert-Bu−C₆H₄S), trans-{RS−(C≡C)_n}₂Ru(dppe)₂ (n=1 ( 1^R ), 2 ( 2^R ); dppe: 1,2-bis(diphenylphosphino)ethane) and trans-(n-C₆H₁₃S−C≡C)₂Ru{P(OMe)₃}₄ 3^hex ] are reported. Scanning tunneling microscope break-junction study has revealed conductance of the organometallic molecular wires with the thioacetylene backbones higher than that of the related organometallic wires having arylethynylruthenium linkages with the sulfur anchor groups, trans-{p-MeS−C₆H₄-(C≡C)_n}₂Ru(phosphine)₄ 4 ⁿ (n=1, 2) and trans-(Th−C≡C)₂Ru(phosphine)₄ 5 (Th=3-thienyl). It should be noted that the molecular junctions constructed from the butadiynyl wire 2^R , trans-{ Au −RS−(C≡C)₂}₂Ru(dppe)₂ ( Au : gold metal electrode), show conductance comparable to that of the covalently linked polyynyl wire with the similar molecular length, trans-{ Au −(C≡C)₃}₂Ru(dppe)₂ 6³ . The DFT non-equilibrium Green's function (NEGF) study supports the highly conducting nature of the thioacetylene molecular wires through HOMO orbitals.     

Synthesis and healing properties of poly(arylether sulfone)–poly(alkylthioether) multiblock copolymers containing disulfide bonds

Thermoplastic elastomers composed of soft and hard segments are important elastic and processable synthetic polymers. The microphase‐separated soft domains show low glass transition temperature and possess sufficient chain mobility at room temperature. In this study, we report the synthesis and healing properties of multiblock copolymers containing disulfide bonds as dynamic covalent bonds. The multiblock copolymers composed of poly(arylether sulfone) and poly(alkylthioether) segments were synthesized by oxidative coupling polymerization of the corresponding thiol‐terminated oligomers. Atomic force microscopy phase images, differential scanning calorimetry, and dynamic mechanical analysis curves indicated the microphase‐separated morphology of the multiblock copolymer. Self‐healing properties of the polymer were evaluated by changes in the elongation at break of the cut/adhered samples. The elongation recovery increased with UV irradiation time, and the multiblock copolymer showed a 93% recovery after UV irradiation for 5 h. The healing efficiency induced by UV irradiation, determined by subtracting the recovery without UV irradiation, was calculated to be 51%. According to the UV spectra and solubility changes after UV irradiation, the main healing factor in this study was the crosslinking reactions caused by thiyl radicals generated from UV irradiation instead of disulfide exchange reactions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3545–3553     

Catalytic Activity of Molybdenum Complexes Bearing PNP-Type Pincer Ligand toward Ammonia Formation

We newly designed and prepared a novel molybdenum complex bearing a 4-[3,5-bis(trifluoromethyl)phenyl]pyridine-based PNP-type pincer ligand, based on the bond dissociation free energies (BDFEs) of the N−H bonds in molybdenum-imide complexes bearing various substituted pyridine-based PNP-type pincer ligands. The complex worked as an excellent catalyst toward ammonia formation from the reaction of an atmospheric pressure of dinitrogen with samarium diiodide as a reductant and water as a proton source under ambient reaction conditions, where up to 3580 equivalents of ammonia were formed based on the molybdenum atom of the catalyst. The catalytic activity was significantly improved by one order of magnitude larger than that observed when using the complex before modification.     

One-Step Synthesis of Cyclobutene-Annulated Fullerenes through a Cascade Reaction

The physicochemical properties of fullerene-based materials typically vary depending on the type and mode of addition of functional groups; therefore, developing fullerene derivatives with novel structures is imperative for further progress in materials science. In this study, we develop an efficient one-step strategy for synthesizing cyclobutene-annulated fullerene derivatives (cyclobutenofullerenes) and characterize their electronic properties. Despite the steric strain, cyclobutenofullerenes can be easily prepared via a one-step reaction of C₆₀ with a secondary propargylic phosphate. Structural analysis of the reaction intermediates suggests that the cascade reaction proceeds through a formal [2+2] cycloaddition of C₆₀ with an allene, caused by the 1,3-migration of the propargylic phosphate, followed by an additional 1,3-migration and the subsequent 1,2-elimination of the phosphodiester moiety.     

ν-Stable τ-Tilting Modules

Inspired by τ-tilting theory [3 Adachi , T. , Iyama , O. , Reiten , I. ( 2014 ). τ-tilting theory . Compos. Math. 150 ( 3 ): 415 – 452 .[Crossref], [Web of Science ®] , [Google Scholar]], we introduce the notion of ν-stable support τ-tilting modules. For any finite dimensional selfinjective algebra Λ, we give bijections between two-term tilting complexes in K ^b (proj Λ), ν-stable support τ-tilting Λ-modules, and ν-stable functorially finite torsion classes in modΛ. Moreover, these objects correspond bijectively to selfinjective cluster tilting objects in 𝒞 if Λ is a 2-CY tilted algebra associated with a Hom-finite 2-CY triangulated category 𝒞. We also study some properties of support τ-tilting modules over 2-CY tilted algebras, and we give a necessary condition such that algebras are 2-CY tilted in terms of support τ-tilting modules.     

Dynamics of water in real space and time

Owing to marked advances in instrumentation in X-ray and neutron scattering the time-dependent pair correlation function, the Van Hove function, can now be determined by inelastic X-ray and neutron scattering measurements. The local dynamics of water in real space and time is visualised by this approach. We discuss how the dynamic properties, such as viscosity and diffusion, can be elucidated through the Van Hove function of water.     

Dimesitylborylethynylated Arenes: Unique Electronic and Photophysical Properties Caused by Ethynediyl (C≡C) Spacers

Herein, we report the synthesis and electrochemical and photophysical properties of aromatic hydrocarbons having one or two dimesitylborylethynyl peripherals. The mono- ( 1 ) and diboryl compounds ( 2 ), readily prepared by nucleophilic substitution reaction, are fairly stable to air and moisture in the solid state. The inserted ethynediyl (C≡C) spacer cancels the steric hindrance between the bulky dimesitylboryl groups and aromatic rings, leading to effective π conjugation over the B−C≡C−Ar linkages, as revealed by cyclic voltammetry. Despite the small structural differences, the photophysical properties of the benzene, naphthalene, and anthracene derivatives are different. Virtually no emission was observed from the benzene derivatives, whereas the anthracene derivatives emitted with high quantum yields both in solution and in the solid state. Notably, the naphthalene derivatives showed aggregation-induced emission behavior. Unlike the common sterically congested triarylborane derivatives reported so far, the anthracene derivatives showed π–π*-type absorption and emission bands, which derive from efficient intramolecular orbital interactions between the boron centers and anthracene moieties, as supported by DFT calculations. As a result, the dimesitylborylethynyl substituents effectively lower the LUMO levels of the aromatic hydrocarbon parts, whereas the HOMO levels are almost unaffected, thereby leading to materials with controllable HOMO–LUMO gaps.