Direct Near Infrared Light–Activatable Phthalocyanine Catalysts

The high penetration of near-infrared (NIR) light makes it effective for use in selective reactions under light-shielded conditions, such as in sealed reactors and deep tissues. Herein, we report the development of phthalocyanine catalysts directly activated by NIR light to transform small organic molecules. The desired photocatalytic properties were achieved in the phthalocyanines by introducing the appropriate peripheral substituents and central metal. These phthalocyanine photocatalysts promote cross-dehydrogenative-coupling (CDC) under irradiation with 810 nm NIR light. The choice of solvent is important, and a mixture of a reaction-accelerating (pyridine) and -decelerating (methanol) solvents was particularly effective. Moreover, we demonstrate photoreactions under visible-light-shielded conditions through the transmission of NIR light. A combined experimental and computational mechanistic analysis revealed that this NIR reaction does not involve a photoredox-type mechanism with electron transfer, but instead a singlet-oxygen-mediated mechanism with energy transfer.     

Enantioselective Synthesis of Chiral Carboxylic Acids from Alkynes and Formic Acid by Nickel-Catalyzed Cascade Reactions: Facile Synthesis of Profens

We report a stereoselective conversion of terminal alkynes to α-chiral carboxylic acids using a nickel-catalyzed domino hydrocarboxylation-transfer hydrogenation reaction. A simple nickel/BenzP* catalyst displayed high activity in both steps of regioselective hydrocarboxylation of alkynes and subsequent asymmetric transfer hydrogenation. The reaction was successfully applied in enantioselective preparation of three nonsteroidal anti-inflammatory profens (>90 % ees) and the chiral fragment of AZD2716.     

Enhancement of Mass and Charge Transfer during Carbon Dioxide Photoreduction by Enhanced Surface Hydrophobicity without a Barrier Layer

The CO₂ reduction reaction (CRR) represents a promising route for the clean utilization of renewable resources. But mass-transfer limitations seriously hinder the forward step. Enhancing the surface hydrophobicity by using polymers has been proved to be one of the most efficient strategies. However, as macromolecular organics, polymers on the surface hinder the transfer of charge carriers from catalysts to reactants. Herein, we describe an in-situ surface fluorination strategy to enhance the surface hydrophobicity of TiO₂ without a barrier layer of organics, thus facilitating the mass transfer of CO₂ to catalysts and charge transfer. With less obstruction to charge transfer, a higher CO_2, and lower H⁺ surface concentration, the photocatalytic CRR generation rate of methanol (CH₃OH) is greatly enhanced to up to 247.15 μmol g⁻¹ h⁻¹. Furthermore, we investigated the overall defects; enhancing the surface hydrophobicity of catalysts provides a general and reliable method to improve the competitiveness of CRR.     

Thermo‐ and pH‐sensitive triblock copolymers with tunable hydrophilic/hydrophobic properties

Polymers consisting of poly(acrylic acid) (PAA) and statistical poly[(acrylic acid)‐co‐(tert‐butylacrylate)] (P(AA‐co‐tBA)), attached to both extremities of Jeffamine® (D series based on a poly(propylene oxide) (PPO) with one amine function at each end) using atom transfer radical polymerization (ATRP) are presented in this article. An original bifunctional amide‐based macroinitiator was first elaborated from Jeffamine®. tBA polymerization was subsequently initiated from this macroinitiator. This polymerization occurs in a well‐controlled manner leading to narrow molecular weights distribution. Amphiphilic copolymers were finally obtained after complete or partial hydrolysis of the PtBA blocks into PAA. The control of the partial hydrolysis of tBA units, conducted in a concentrated HCl/tetrahydrofuran mixture, is demonstrated. The properties of the triblock copolymers were preliminary investigated in aqueous solution by absorbance, DLS measurements and SEC/MALS/DV/DRI analysis as a function of temperature and pH modifications, providing evidences of thermo‐ and pH‐sensitive self‐assembly of the copolymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2606–2616     

A new Monte Carlo model for predicting the mechanical properties of fiber yarns

Understanding the complicated failure mechanisms of hierarchical composites such as fiber yarns is essential for advanced materials design. In this study, we developed a new Monte Carlo model for predicting the mechanical properties of fiber yarns that includes statistical variation in fiber strength. Furthermore, a statistical shear load transfer law based on the shear lag analysis was derived and implemented to simulate the interactions between adjacent fibers and provide a more accurate tensile stress distribution along the overlap distance. Simulations on two types of yarns, made from different raw materials and based on distinct processing approaches, predict yarn strength values that compare favorably with experimental measurements. Furthermore, the model identified very distinct dominant failure mechanisms for the two materials, providing important insights into design features that can improve yarn strength.     

Synthesis,Electrochemistry, and Photophysical Studies of Ruthenium(II) Polypyridine Complexes with D–π–A–π–D Type Ligands and Their Application Studies as Organic Memories

A new class of ruthenium(II) polypyridine complexes with a series of D–π–A–π–D type (D=donor, A=acceptor) ligands was synthesized and characterized by ¹H NMR spectroscopy, mass spectrometry, and elemental analysis. The photophysical and electrochemical properties of the complexes were also investigated. The newly synthesized ruthenium(II) polypyridine complexes were found to exhibit two intense absorption bands at both high‐energy (λ=333–369 nm) and low‐energy (λ=520–535 nm) regions. They are assigned as intraligand (IL) π→π* transitions of the bipyridine (bpy) and π‐conjugated bpy ligands, and IL charge‐transfer (CT) transitions from the donor to the acceptor moiety with mixing of dπ(Ru^II)→π*(bpy) and dπ(Ru^II)→π*(L) MLCT characters, respectively. In addition, all complexes were demonstrated to exhibit intense red emissions at approximately λ=727–744 nm in degassed dichloromethane at 298 K or in n‐butyronitrile glass at 77 K. Nanosecond transient absorption (TA) spectroscopy has also been carried out, establishing the presence of the charge‐separated state. In order to understand the electrochemical properties of the complexes, cyclic voltammetry has also been performed. Two quasi‐reversible oxidation couples and three quasi‐reversible reduction couples were observed. One of the ruthenium(II) complexes has been utilized in the fabrication of memory devices, in which an ON/OFF current ratio of over 10⁴ was obtained.     

Synthesis,Electrochemistry, and Photophysics of Aza‐BODIPY Porphyrin Dyes

The synthesis of dyad and triad aza‐BODIPY‐porphyrin systems in two steps starting from an aryl‐substituted aza‐BODIPY chromophore is described. The properties of the resulting aza‐BODIPY‐porphyrin conjugates have been extensively investigated by means of electrochemistry, spectroelectrochemistry, and absorption/emission spectroscopy. Fluorescence measurements have revealed a dramatic loss of luminescence intensity, mainly due to competitive energy transfer and photoinduced electron transfer involving charge separation followed by recombination.     

Proton transfer-assisted host–guest complexation between a difunctional pillar[5]arene and amine-based guests

Proton transfer from a difunctional pillar[5]arene containing two carboxylic acid moieties to amine-based guests occurs in the host–guest complexation. The binding affinities are enhanced effectively due to the existence of electrostatic interactions.     

Carbon fibers prepared from tailored reversible‐addition‐fragmentation transfer copolymerization‐derived poly(acrylonitrile)‐co‐poly(methylmethacrylate)

Reversible‐addition fragmentation‐transfer (RAFT) polymerization of acrylonitrile (AN) was performed with 2‐(2‐cyano‐2‐propyl‐dodecyl)trithiocarbonate as RAFT agent and azobis(isobutyronitrile) as initiator. Linear polyacrylonitrile (M_n = 133,000 g/mol, PDI = 1.34) was prepared within 7 h in 86% isolated yield. High‐yield copolymerization with methyl methacrylate (MMA) was performed and copolymerization parameters were determined according to Kelen and Tüdös at 90 °C in ethylene carbonate yielding r_AN = 0.2 and r_MMA = 0.42. The molecular weights, polydispersity indices (PDIs), and MMA content of the copolymer were adjusted in a way that precursor fibers could be prepared via wet spinning. These precursor fibers had round cross‐sections and a dense morphology, showing tenacities of 40–50 cN/tex and elastic moduli of 900–1000 cN/tex at a fineness of 1 dtex and an elongation of 13–17%. Precursor fibers were oxidatively stabilized and then carbonized at different temperatures. A maximum tensile strength of 2.5 GPa was reached at 1350 °C. Thermal analysis, infrared and Raman spectroscopy, wide‐angle X‐ray scattering, scanning electron microscopy, and tensile testing were used to characterize the resulting carbon fibers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1322–1333     

Electrolytes for quasi solid‐state dye‐sensitized solar cells based on block copolymers

The first use of PS_n‐b‐PEO_m‐b‐PS_n block copolymers (PS = polystyrene, PEO = poly(ethylene oxide)) as solid hosts for iodine/iodide electrolytes in dye‐sensitized solar cells (DSSCs) is described. Using the benchmark photosensitizer N719, DSSC based on the quasi solid‐state electrolytes afforded efficiencies up to 6.7%, to be compared with an efficiency of 7.3% obtained in similar conditions with a conventional iodine/iodide liquid electrolyte. By varying the PS:PEO relative volume ratio in the block copolymers different properties and morphologies were obtained. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 719–727