Nanographenes, or extended polycyclic aromatic hydrocarbons, have been attracting renewed and more widespread attention since the first experimental demonstration of graphene in 2004. However, the atomically precise fabrication of nanographenes has thus far been achieved only through synthetic organic chemistry. The precise synthesis of quasi-zero-dimensional nanographenes, i.e. graphene molecules, has witnessed rapid developments over the past few years, and these developments can be summarized in four categories: (1) non-conventional methods, (2) structures incorporating seven- or eight-membered rings, (3) selective heteroatom doping, and (4) direct edge functionalization. On the other hand, one-dimensional extension of the graphene molecules leads to the formation of graphene nanoribbons (GNRs) with high aspect ratios. The synthesis of structurally well-defined GNRs has been achieved by extending nanographene synthesis to longitudinally extended polymeric systems. Access to GNRs thus becomes possible through the solution-mediated or surface-assisted cyclodehydrogenation, or “graphitization,” of tailor-made polyphenylene precursors. In this review, we describe recent progress in the “bottom-up” chemical syntheses of structurally well-defined nanographenes, namely graphene molecules and GNRs.

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New advances in nanographene chemistry

Oxidative Coupling between Two Hydrocarbons: An Update of Recent C–H Functionalizations

Transition metal-mediated C–H bond activation and functionalization represent one of the most straightforward and powerful tools in modern organic synthetic chemistry. Bi(hetero)aryls are privileged π-conjugated structural cores in biologically active molecules, organic functional materials, ligands, and organic synthetic intermediates. The oxidative C–H/C–H coupling reactions between two (hetero)arenes through 2-fold C–H activation offer a valuable opportunity for rapid assembly of diverse bi(hetero)aryls and further exploitation of their applications in pharmaceutical and material sciences. This review provides a comprehensive overview of the fundamentals and applications of transition metal-mediated/catalyzed oxidative C–H/C–H coupling reactions between two (hetero)arenes. The substrate scope, limitation, reaction mechanism, regioselectivity, and chemoselectivity, as well as related control strategies of these reactions are discussed. Additionally, the applications of these established methods in the s...

Oxidative C-H/C-H Coupling Reactions between Two (Hetero)arenes.

Unperturbed dimensions of stereoregular polymers.- Reinforcement of rubber by carbon black.- Transformations of phenolic antioxidants and the role of their products in the long-term properties of polyolefins.

Properties of polymers

Does the dehydrogenative coupling of aromatic compounds mediated by AlCl3 at high temperatures and also by FeCl3, MoCl5, PIFA, or K3[Fe(CN)6] at room temperature proceed by the same mechanism in all cases? With the growing importance of the synthesis of aromatic compounds by double C-H activation to give various biaryl structures, this question becomes pressing. Since some of these reactions proceed only in the presence of non-oxidizing Lewis acids and some only in the presence of certain oxidants, the authors venture the hypothesis that, depending on the electronic structure of the substrates and the nature of the "catalyst", two different mechanisms can operate. One involves the intermediacy of a radical cation and the other the formation of a sigma complex between the acid and the substrate. The goal of this Review is to encourage further mechanistic studies hopefully leading to an in-depth understanding of this phenomenon.

Comparison of Oxidative Aromatic Coupling and the Scholl Reaction

Oxidative transformation of aryls using molybdenum pentachloride

We introduce the design of Janus-type paper sheets where one side of the paper exhibits superhydrophobic properties, whereas the other side of the sheet remains hydrophilic and therefore can take up aqueous solutions by capillary wicking. Such papers are being prepared by chemically immobilizing a thin hybrid coating on paper sheets that consists of cross-linked poly(dimethylsiloxane) (PDMS) and inorganic particles of various sizes ranging from nanometers to several tens of micrometers. Both commercially available Whatman No. 1 filter paper and lab-engineered cotton linters-based paper substrates were treated with this approach. The hybrid paper sheets have high chemical durability, mechanical stability, and flexibility because of a covalent attachment of the particles to paper fibers and the inherent elasticity of PDMS chains. In spite of the superhydrophobicity of the coating, the untreated side of the paper substrates preserved its hydrophilicity, resulting in Janus-type wetting and wicking properties, respectively. The functionalized paper samples remained porous and permeable to gases, while possessing a gradual change in chemistry between the two sides exhibiting a dramatic wetting contrast. Such two-sided properties open up new applications for such hybrid paper materials, such as in wound dressings and/or bandages with a liquid directing and confinement ability.

Superhydrophobic Hybrid Paper Sheets with Janus-Type Wettability.

Versatile oxidative approach to carbazoles and related compounds using MoCl5.

In recent years, Janus interface materials with wettability contrast have attracted remarkable attention because of their beneficial properties and versatile potential applications in materials sci...

Simon Trosien

Papers

Oxidative transformation of aryls using molybdenum pentachloride

Superhydrophobic Hybrid Paper Sheets with Janus-Type Wettability.

Versatile oxidative approach to carbazoles and related compounds using MoCl5.

Janus Interface Materials: A Critical Review and Comparative Study

Synthesis of Highly Functionalized 9,10-Phenanthrenequinones by Oxidative Coupling Using MoCl5