Evaluation of reaction spontaneity for acidic and reductive dissolutions of corrosion metal oxides using HyBRID chemical decontamination

Journal of Radioanalytical and Nuclear Chemistry - Complete sets of reaction mechanisms are proposed in the acidic and reductive dissolution of magnetite, nickel ferrite, and chromite using the...     

Transition-Metal Catalysis of Triene 6π Electrocyclization: The π-Complexation Strategy Realized

Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C₅H₅)Ru(NCMe)₃]PF₆ as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations.     

Precisely Controlled Multidimensional Covalent Frameworks: Polymerization of Supramolecular Colloids

Rapid and selective removal of micropollutants from water is important for the reuse of water resources. Despite hollow frameworks with specific functionalized porous walls for the selective adsorption based on a series of interactions, tailoring a stable shape of nanometer- and micrometer-sized architectures for the removal of specific pollutants remains a challenge. Here, exactly controlled sheets, tubes, and spherical frameworks were presented from the crosslinking of supramolecular colloids in polar solvents. The frameworks strongly depended on the architecture of original supramolecular colloids. As the entropy of colloids increased, the initial laminar framework rolled up into hollow tubules, and then further curled into hollow spheres. These shape-persistent frameworks showed unprecedented selectivity as well as specific recognition for the shape of pollutants, thus contributing to efficient pollutant separation.     

6-(Hetero)arylindolizino[1,2-c]quinolines as highly fluorescent chemical space: Synthesis and photophysical properties

A highly fluorescent indolizino[1,2-c]quinoline with a substituent at the C6 position was designed and synthesized as a new indolizine-quinoline hybrid structure via a tetracyclic lactam. Various (hetero)aryl groups were introduced at the C6 site of this basic skeleton to display intriguing photophysical properties.     

Divergent strategy for the synthesis of bottlebrush polymers via postpolymerization modification of macromonomer

A simple and divergent synthetic strategy of bottlebrush polymers (BBPs) is presented, consisting of postpolymerization modification of a macromonomer and grafting-through polymerization. Beginning with a single macromonomer, its direct modification could build a library of macromonomers with an identical chain length, thus guaranteeing the precision in the synthesis of BBPs. In this study, a newly designed norbornenyl-terminated poly(methyl acrylate) (NB-PMA) is proposed as a chemically robust template. Ti-mediated transesterification of NB-PMA successfully produces structurally diverse polyacrylates while maintaining the terminal norbornenyl group intact. All macromonomers obtained from transesterification possess a good grafting-through ring-opening metathesis polymerization reactivity, furnishing homo, random, and block BBPs in a controllable manner. Moreover, atomic force microscopy analysis supports the controlled side-chain length distribution in the resulting BBPs.     

Stoichiometry-Controlled Synthesis of Nanoparticulate Mixed-Metal Oxyhydroxide Oxygen Evolving Catalysts by Electrochemistry in Aqueous Nanodroplets

Mixed-metal oxyhydroxides—especially those of Ni and Fe—are one of the most active classes of materials known for catalyzing the oxygen evolution reaction (OER). Here, nanoparticulate mixed metal oxyhydroxides (of Ni, Fe, and Co) were prepared on an electrode surface by electrochemical reaction of a precursor solution encapsulated in aqueous nanodroplets (AnDs), with each of the droplets containing 10 s of attoliters of fluid. Electrode reactions and synthesis can be monitored in situ by electrochemistry as single AnD stochastically lands and interacts with the working electrode. Resultant metal oxyhydroxide nanoparticles can be size and composition controlled precisely by modulating the precursor solution stored in the AnD. Nanoparticulate metal oxyhydroxides were implemented as catalysts for the OER and exhibited superior catalysis compared to their thin-film counterparts, demonstrating a hundred-thousand-fold enhancement in atom efficiency at comparable turnover rates.     

Molybdenum Disulfide Based Nanomaterials for Rechargeable Batteries

The rapid development of electrochemical energy storage systems requires new electrode materials with high performance. As a two-dimensional material, molybdenum disulfide (MoS₂) has attracted increasing interest in energy storage applications due to its layered structure, tunable physical and chemical properties, and high capacity. In this review, the atomic structures and properties of different phases of MoS₂ are first introduced. Then, typical synthetic methods for MoS₂ and MoS₂-based composites are presented. Furthermore, the recent progress in the design of diverse MoS₂-based micro/nanostructures for rechargeable batteries, including lithium-ion, lithium-sulfur, sodium-ion, potassium-ion, and multivalent-ion batteries, is overviewed. Additionally, the roles of advanced in situ/operando techniques and theoretical calculations in elucidating fundamental insights into the structural and electrochemical processes taking place in these materials during battery operation are illustrated. Finally, a perspective is given on how the properties of MoS₂-based electrode materials are further improved and how they can find widespread application in the next-generation electrochemical energy-storage systems.     

Organic Cage Dumbbells

Molecular dumbbells with organic cage capping units were synthesised via a multi-component imine condensation between a tri-topic amine and di- and tetra-topic aldehydes. This is an example of self-sorting, which can be rationalised by computational modelling.     

Exfoliation of 2D Materials for Energy and Environmental Applications

The fascinating properties of single-layer graphene isolated by mechanical exfoliation have inspired extensive research efforts toward two-dimensional (2D) materials. Layered compounds serve as precursors for atomically thin 2D materials (briefly, 2D nanomaterials) owing to their strong intraplane chemical bonding but weak interplane van der Waals interactions. There are newly emerging 2D materials beyond graphene, and it is becoming increasingly important to develop cost-effective, scalable methods for producing 2D nanomaterials with controlled microstructures and properties. The variety of developed synthetic techniques can be categorized into two classes: bottom-up and top-down approaches. Of top-down approaches, the exfoliation of bulk 2D materials into single or few layers is the most common. This review highlights chemical and physical exfoliation methods that allow for the production of 2D nanomaterials in large quantities. In addition, remarkable examples of utilizing exfoliated 2D nanomaterials in energy and environmental applications are introduced.     

Noncovalent Intermolecular Interaction in Cofacially Stacked 24π Antiaromatic Hexaphyrin Dimer

π–π Stacking is omnipresent not only in nature but in a wide variety of practical fields applied to our lives. Because of its importance in a performance of natural and artificial systems, such as light harvesting system and working layer in device, many researchers have put intensive effort into identifying its underlying nature. However, for the case of π–π stacked systems composed of antiaromatic units, the understanding of the fundamental mechanisms is still unclear. Herein, we synthesized a new type of planar β,β’-phenylene-bridged hexaphyrin (1.0.1.0.1.0), referred as naphthorosarin which possesses the 24π-electron conjugated pathway. Especially, the corresponding antiaromatic porphyrinoid shows the unique property to form dimeric species adopting the face-to-face geometry which is unprecedented in cases of known annulated naphthorosarins. In order to elucidate the intriguing properties derived from the stacked dimer, the current study focuses on the experimental support to rationalize the observed π–π interactions between the two subunits.