Decacyclene Radical Anions Showing Strong Low‐energy Intramolecular Absorption and Magnetic Coupling of Spins in a Hexagonal Network

Two salts of the aromatic hydrocarbon decacyclene, {cryptand[2.2.2](Cs⁺)} (decacyclene^.?) ( 1 ) and {Bu₃MeP⁺}(decacyclene^.?) ( 2 ), were obtained. In both salts, decacyclene^.? radical anions formed channels occupied by cations. However, corrugated hexagonal decacyclene^.? layers could be outlined in the crystal structure of 1 with several side‐by‐side C???C approaches. The decacyclene^.? radical anions showed strong distortion in both salts, deviating from the C₃ symmetry owing to the repulsion of closely arranged hydrogen atoms and the Jahn‐Teller effect. Radical anions showed intense unusually low energy absorption in the IR‐range, with maxima at 4800 and 6000 cm^?1. According to the carculations, these bands can originate from the SOMO‐LUMO+1 and SOMO‐LUMO+2 transitions, respectively. Radical anions exhibited a S=1/2 spin state, with an effective magnetic moment of 1.72 μ_B at 300 K. The decacyclene^.? spin antiferromagnetically coupled with a Weiss temperature of ?11 K. Spin ordering was not observed down to 1.9 K owing to spin frustration in the hexagonal decacyclene^.? layers.     

Engineering nanostructures of CuO-based photocatalysts for water treatment: Current progress and future challenges

Nowadays, increasing extortions regarding environmental problems and energy scarcity have stuck the development and endurance of human society. The issue of inorganic and organic pollutants that exist in water from agricultural, domestic, and industrial activities has directed the development of advanced technologies to address the challenges of water scarcity efficiently. To solve this major issue, various scientists and researchers are looking for novel and effective technologies that can efficiently remove pollutants from wastewater. Nanoscale metal oxide materials have been proposed due to their distinctive size, physical and chemical properties along with promising applications. Cupric Oxide (CuO) is one of the most commonly used benchmark photocatalysts in photodegradation owing to the fact that they are cost-effective, non-toxic, and more efficient in absorption across a significant fraction of solar spectrum. In this review, we have summarized synthetic strategies of CuO fabrication, modification methods with applications for water treatment purposes. Moreover, an elaborative discussion on feasible strategies includes; binary and ternary heterojunction formation, Z-scheme based photocatalytic system, incorporation of rare earth/transition metal ions as dopants, and carbonaceous materials serving as a support system. The mechanistic insight inferring photo-induced charge separation and transfer, the functional reactive radical species involved in a photocatalytic reaction, have been successfully featured and examined. Finally, a conclusive remark regarding current studies and unresolved challenges related to CuO are put forth for future perspectives.     

Synthesis and radical polymerization of acrylate and methacrylate bearing an isocyanurate core with adamantyl bisurethane moieties

In this article, we report the synthesis of acrylate and methacrylate bearing an isocyanurate core with two adamantyl urethane moieties and their radical homo- and copolymerization with n-butyl methacrylate (BMA). The synthesized polyacrylate exhibits higher 5% weight loss and glass transition temperatures (T_d5 and T_g) than those of the comparative polyacrylate, synthesized from the isocyanurate-based acrylate with two hexyl urethane moieties, suggesting that the rigid adamantane core incorporated in the side chains of polymer largely contributes to increase in thermal stability of polymer. Similarly, the obtained copolymers show higher T_g values than that of homopolymer derived from BMA, leading to the synthesized monomers are useful as a comonomer to enhance thermal property of polymer.     

Copper‐Catalyzed Difunctionalization of Activated Alkynes by Radical Oxidation–Tandem Cyclization/Dearomatization to Synthesize 3‐Trifluoromethyl Spiro[4.5]trienones

A copper‐catalyzed difunctionalizing trifluoromethylation of activated alkynes with the cheap reagent sodium trifluoromethanesulfinate (NaSO₂CF₃ or Langlois’ reagent) has been developed incorporating a tandem cyclization/dearomatization process. This strategy affords a straightforward route to synthesis of 3‐(trifluoromethyl)‐spiro[4.5]trienones, and presents an example of difunctionalization of alkynes for simultaneous formation of two carbon–carbon single bonds and one carbon–oxygen double bond.     

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     

Copper-catalyzed methyl esterification of aromatic aldehydes and benzoic alcohols by TBHP as both oxidant and methyl source

A copper-catalyzed synthesis of methyl esters from aromatic aldehydes in the presence of tert-butyl hydrogen peroxide (TBHP) was developed via a radical reaction mechanism. TBHP acts not only as an efficient oxidant, but also as a green methyl source in such transformation. Moreover, this method could also be efficiently extended to the methyl esterification of benzylic alcohols.     

Autonomous conveyer gel driven by frontal polymerization

Autonomous mechanical mass transportation for cargos on the microscale with no need of continuous external powering is of great scientific and technological interest due to their extensive applications. However, it is still challenging to create a self‐driven system applicable to diverse micromaterial transportation demands. In this work, we developed a novel autonomous conveyer gel driven by frontal polymerization (FP). The chemical wave produced in FP was stable, and self‐propagating with a constant velocity, which can be easily monitored by thermal imaging or fluorescence labeling. We investigated the influence of the initiation temperature, swelling ratio of the gel substrate, and the size of the cargos on the motion of driven behavior. Results showed that the driving velocity can be well controlled by altering the initiation temperatures of FP. The swelling ratio and the size of the cargos had a key impact on the feasibility of self‐driven behavior. In addition, powerful driven capability by FP was demonstrated by successfully transporting cargos in series, and further applied for targeted synthesis of CdS nanocrystals. The methodology developed here provides an effective way to convert chemical energy to mechanical work, and may be useful in energy conversion and utilization, mass transportation and other applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1323‐1331