Carbon Nanosheets by Morphology‐Retained Carbonization of Two‐Dimensional Assembled Anisotropic Carbon Nanorings

Two‐dimensional (2D) carbon nanomaterials possessing promising physical and chemical properties find applications in high‐performance energy storage devices and catalysts. However, large‐scale fabrication of 2D carbon nanostructures is based on a few specific carbon templates or precursors and poses a formidable challenge. Now a new bottom‐up method for carbon nanosheet fabrication using a newly designed anisotropic carbon nanoring molecule, CPPhen, is presented. CPPhen was self‐assembled at a dynamic air–water interface with a vortex motion to afford molecular nanosheets, which were then carbonized under inert gas flow. Their nanosheet morphologies were retained after carbonization, which has never been seen for low‐molecular weight compounds. Furthermore, adding pyridine as a nitrogen dopant in the self‐assembly step successfully afforded nitrogen‐doped carbon nanosheets containing mainly pyridinic nitrogen species.     

N‐Doped Carbon Aerogel Derived from a Metal–Organic Framework Foam as an Efficient Electrocatalyst for Oxygen Reduction

Metal–organic frameworks (MOFs) are promising alternative precursors for the fabrication of heteroatom‐doped carbon materials for energy storage and conversion. However, the direct pyrolysis of bulk MOFs usually gives microporous carbonaceous materials, which significantly hinder the mass transportation and the accessibility of active sites. Herein, N‐doped carbon aerogels with hierarchical micro‐, meso‐, and macropores were fabricated through one‐step pyrolysis of zeolitic imidazolate framework‐8/carboxymethylcellulose composite gel. Owing to the hierarchical porosity, high specific surface area, favorable conductivity, excellent thermal and chemical stability, the as‐prepared N‐doped carbon aerogel exhibits excellent oxygen reduction reaction (ORR) activity, long‐term durability, and good methanol tolerance in alkaline medium. This work thus provides a new way to fabricate new types of MOF‐derived carbon aerogels for various applications.     

Microfluidic Synthesis Enables Dense and Uniform Loading of Surfactant‐Free PtSn Nanocrystals on Carbon Supports for Enhanced Ethanol Oxidation

Developing new synthetic methods for carbon supported catalysts with improved performance is of fundamental importance in advancing proton exchange membrane fuel cell (PEMFC) technology. Continuous‐flow, microfluidic reactions in capillary tube reactors are described, which are capable of synthesizing surfactant‐free, ultrafine PtSn alloyed nanoparticles (NPs) on various carbon supports (for example, commercial carbon black particles, carbon nanotubes, and graphene sheets). The PtSn NPs are highly crystalline with sizes smaller than 2 nm, and they are highly dispersed on the carbon supports with high loadings up to 33 wt %. These characteristics make the as‐synthesized carbon‐supported PtSn NPs more efficient than state of the art commercial Pt/C catalysts applied to the ethanol oxidation reaction (EOR). Significantly enhanced mass catalytic activity (two‐times that of Pt/C) and improved stability are obtained.     

Visible‐Light‐Induced Nickel‐Catalyzed Negishi Cross‐Couplings by Exogenous‐Photosensitizer‐Free Photocatalysis

The merging of photoredox and transition‐metal catalysis has become one of the most attractive approaches for carbon–carbon bond formation. Such reactions require the use of two organo‐transition‐metal species, one of which acts as a photosensitizer and the other one as a cross‐coupling catalyst. We report herein an exogenous‐photosensitizer‐free photocatalytic process for the formation of carbon–carbon bonds by direct acceleration of the well‐known nickel‐catalyzed Negishi cross‐coupling that is based on the use of two naturally abundant metals. This finding will open new avenues in cross‐coupling chemistry that involve the direct visible‐light absorption of organometallic catalytic complexes.     

Tunable Photoluminescence Across the Entire Visible Spectrum from Carbon Dots Excited by White Light

Although reports have shown shifts in carbon dot emission wavelengths resulting from varying the excitation wavelength, this excitation‐dependent emission does not constitute true tuning, as the shifted peaks have much weaker intensity than their dominant emission, and this is often undesired in real world applications. We report for the first time the synthesis and photoluminescence properties of carbon dots whose peak fluorescence emission wavelengths are tunable across the entire visible spectrum by simple adjustment of the reagents and synthesis conditions, and these carbon dots are excited by white light. Detailed material characterization has revealed that this tunable emission results from changes in the carbon dots’ chemical composition, dictated by dehydrogenation reactions occurring during carbonization. These significantly alter the nucleation and growth process, resulting in dots with either more oxygen‐containing or nitrogen‐containing groups that ultimately determine their photoluminescence properties, which is in stark contrast to previous observations of carbon dot excitation‐dependent fluorescence. This new ability to synthesize broadband excitable carbon dots with tunable peak emissions opens up many new possibilities, particularly in multimodal sensing, in which multiple analytes and processes could be monitored simultaneously by associating a particular carbon dot emission wavelength to a specific chemical process without the need for tuning the excitation source.     

Hierarchical Structures of Carbon Nanotubes and Arrays of Chromium‐Capped Silicon Nanopillars: Formation and Electrical Properties

The formation of stochastically oriented carbon‐nanotube networks on top of an array of free‐standing chromium‐capped silicon nanopillars is reported. The combination of nanosphere lithography and chemical vapor deposition enables the construction of nanostructures that exhibit a hierarchical sequence of structural sizes. Metallic chromium serves as an etching mask for Si‐pillar formation and as a nucleation site for the formation of carbon nanotubes through the chemical vapor deposition of ethene, ethanol, and methane, respectively, thereby bridging individual pillars from top to top. Iron and cobalt were applied onto the chromium caps as catalysts for CNT growth and the influence of different carbon sources and different gas‐flow rates were investigated. The carbon nanotubes were structurally characterized and their DC electrical properties were studied by in situ local‐ and ex situ macroscopic measurements, both of which reveal their semiconductor properties. This process demonstrates how carbon nanotubes can be integrated into Si‐based semiconductors and, thus, this process may be used to form high‐surface‐area sensors or new porous catalyst supports with enhanced gas‐permeation properties.     

Diastereoselective Construction of Densely Functionalized 1‐Halocyclopentenes Using an Alkynyl Halo‐Prins/Halo‐Nazarov Cyclization Strategy

A diastereoselective two‐step strategy for the synthesis of densely functionalized 1‐halocyclopentenes with several chiral centers has been developed. In the first step, a multicomponent alkynyl halo‐Prins reaction joins an enyne, a carbonyl derivative, and either a chloride, bromide, or iodide to produce a cyclic ether intermediate. In the subsequent step, the intermediate is ionized to generate a halopentadienyl cation, which undergoes an interrupted halo‐Nazarov cyclization. The products contain three new contiguous stereogenic centers, generated with a high level of stereocontrol, as well as a vinyl halide allowing for additional functionalization. The strategy creates two new carbon–carbon bonds, one carbon–halide bond, and one carbon–oxygen bond.     

Light Harvesting and White‐Light Generation in a Composite of Carbon Dots and Dye‐Encapsulated BSA‐Protein‐Capped Gold Nanoclusters

Several strategies have been adopted to design an artificial light‐harvesting system in which light energy is captured by peripheral chromophores and it is subsequently transferred to the core via energy transfer. A composite of carbon dots and dye‐encapsulated BSA‐protein‐capped gold nanoclusters (AuNCs) has been developed for efficient light harvesting and white light generation. Carbon dots (C‐dots) act as donor and AuNCs capped with BSA protein act as acceptor. Analysis reveals that energy transfer increases from 63 % to 83 % in presence of coumarin dye (C153), which enhances the cascade energy transfer from carbon dots to AuNCs. Bright white light emission with a quantum yield of 19 % under the 375 nm excitation wavelength is achieved by changing the ratio of components. Interesting findings reveal that the efficient energy transfer in carbon‐dot–metal‐cluster nanocomposites may open up new possibilities in designing artificial light harvesting systems for future applications.     

Π‐Stacking Functionalization of Carbon Nanotubes through Micelle Swelling

We report on a new, original and efficient method for π‐stacking functionalization of single‐wall carbon nanotubes. This method is applied to the synthesis of a high‐yield light‐harvesting system combining single‐wall carbon nanotubes and porphyrin molecules. We developed a micelle‐swelling technique that leads to controlled and stable complexes presenting an efficient energy transfer. We demonstrate the key role of the organic solvent in the functionalization mechanism. By swelling the micelles, the solvent helps the non‐water‐soluble porphyrins to reach the micelle core and allows a strong enhancement of the interaction between porphyrins and nanotubes. This technique opens new avenues for the functionalization of carbon nanostructures.     

Synthesis,Structural Characterization and Preliminary Biological Studies of Several Heterocyclic Transition Metal Carbonyl Complexes

The reaction of molybdenum, tungsten and manganese carbonyls with several thiazole heterocycle ligands yielded a number of coordinated transition metal complexes 1 – 10 . Of these complexes 1 – 6 are new compounds which have not been reported to date. The structures of new compounds were characterized by FT‐IR and ¹H‐NMR spectroscopy as well as single‐crystal X‐ray diffraction analysis. Complexes 1 – 10 are carbon monoxide releasing molecules that show structure‐related anti‐cancer activity. The cytotoxicity of all compounds on Hela cells was evaluated by MTT assay, and the results show that carbon monoxide releasing molecules containing such Schiff base ligands may have biomedical applications for their anti‐tumor effect.     

Cyanoalkylation: Alkylnitriles in Catalytic CC Bond‐Forming Reactions

Alkylnitriles are one of the most ubiquitous nitrogen‐containing chemicals and are widely employed in reactions which result in nitrile‐group conversion into other functionalities. Nevertheless, their use as carbon pronucleophiles in carbon–carbon bond‐forming reactions has been hampered by difficulties associated mainly with the catalytic generation of active species, that is, α‐cyano carbanions or metalated nitriles. Recent investigations have addressed this challenge and have resulted in different modes of alkylnitrile activation. This review illustrates these findings, which have set the foundation for the development of practical and conceptually new catalytic, direct cyanoalkylation methodologies.     

Cyclic Alkyne Approach to Heteroatom‐Containing Polycyclic Aromatic Hydrocarbon Scaffolds

We report a modular synthetic strategy for accessing heteroatom‐containing polycyclic aromatic hydrocarbons (PAHs). Our approach relies on the controlled generation of transient heterocyclic alkynes and arynes. The strained intermediates undergo in situ trapping with readily accessible oxadiazinones. Four sequential pericyclic reactions occur, namely two Diels–Alder/retro‐Diels–Alder sequences, which can be performed in a stepwise or one‐pot fashion to assemble four new carbon–carbon (C?C) bonds. These studies underscore how the use of heterocyclic strained intermediates can be harnessed for the preparation of new organic materials.     

Intercrossed Carbon Nanorings with Pure Surface States as Low‐Cost and Environment‐Friendly Phosphors for White‐Light‐Emitting Diodes

As an important energy‐saving technique, white‐light‐emitting diodes (W‐LEDs) have been seeking for low‐cost and environment‐friendly substitutes for rare‐earth‐based expensive phosphors or Pd²⁺/Cd²⁺‐based toxic quantum dots (QDs). In this work, precursors and chemical processes were elaborately designed to synthesize intercrossed carbon nanorings (IC‐CNRs) with relatively pure hydroxy surface states for the first time, which enable them to overcome the aggregation‐induced quenching (AIQ) effect, and to emit stable yellow‐orange luminescence in both colloidal and solid states. As a direct benefit of such scarce solid luminescence from carbon nanomaterials, W‐LEDs with color coordinate at (0.28, 0.27), which is close to pure white light (0.33, 0.33), were achieved through using these low‐temperature‐synthesized and toxic ion‐free IC‐CNRs as solid phosphors on blue LED chips. This work demonstrates that the design of surface states plays a crucial role in exploring new functions of fluorescent carbon nanomaterials.     

Aromatic Chemistry in the Excited State: Facilitating Metal‐Free Substitutions and Cross‐Couplings

Transition‐metal‐catalyzed cross‐couplings between aromatic electrophiles and nucleophiles have revolutionized modern chemical syntheses. Nevertheless, transition‐metal‐free approaches are preferable, considering the various issues caused by metal catalysts. This Minireview summarizes the recent progress in the light‐enabled transition‐metal‐free formation of carbon–carbon and carbon–heteroatom bonds in aromatics, which opens a new avenue in aromatic reactions. From the mechanistic perspective, it classifies different reaction types of aryl electrophiles in an excited state with various nucleophiles. We believe this will provide more rationales for metal‐free aromatic substitutions and cross‐couplings with light, and guide the development of novel transformations of aromatic compounds facilitated by light.     

A 3D Organically Synthesized Porous Carbon Material for Lithium‐Ion Batteries

We report the first organically synthesized sp–sp³ hybridized porous carbon, OSPC‐1. This new carbon shows electron conductivity, high porosity, the highest uptake of lithium ions of any carbon material to‐date, and the ability to inhibit dangerous lithium dendrite formation. The new carbon exhibits exceptional potential as anode material for lithium‐ion batteries (LIBs) with high capacity, excellent rate capability, long cycle life, and potential for improved safety performance.     

Azocinoindole Synthesis by a Gold(I)‐Catalyzed Ring Expansion of 2‐Propargyl‐β‐Tetrahydrocarboline

A new methodology taking advantage of gold(I)‐catalyzed ring expansion has been developed to assemble tricyclic 1H‐azocino[5,4‐b]indoles from 2‐propargyl‐β‐tetrahydrocarbolines. The azocinoindoles were obtained in moderate to excellent yields; the structure of which was established by X‐ray crystallographic analysis. A mechanism involving regioselective intramolecular hydroarylation, [1,2]‐alkenyl migration and carbon–carbon bond‐fragmentation was proposed.     

Water‐Enabled Catalytic Asymmetric Michael Reactions of Unreactive Nitroalkenes: One‐Pot Synthesis of Chiral GABA‐Analogs with All‐Carbon Quaternary Stereogenic Centers

Water enables new catalytic reactions for otherwise unreactive substrate systems. Under the “on water” reaction conditions, extremely unreactive β,β‐disubstituted nitroalkenes smoothly underwent enantioselective Michael addition reactions with dithiomalonates using a chiral squaramide catalyst, affording both enantiomers of highly enantioenriched Michael adducts with all‐carbon‐substituted quaternary centers. The developed “on water” protocol was successfully applied for the scalable one‐pot syntheses of chiral GABA analogs with all‐carbon quaternary stereogenic centers at the β‐position, which might show highly interesting pharmaceutical properties.     

Wood‐Derived Ultrathin Carbon Nanofiber Aerogels

Carbon aerogels with 3D networks of interconnected nanometer‐sized particles exhibit fascinating physical properties and show great application potential. Efficient and sustainable methods are required to produce high‐performance carbon aerogels on a large scale to boost their practical applications. An economical and sustainable method is now developed for the synthesis of ultrathin carbon nanofiber (CNF) aerogels from the wood‐based nanofibrillated cellulose (NFC) aerogels via a catalytic pyrolysis process, which guarantees high carbon residual and well maintenance of the nanofibrous morphology during thermal decomposition of the NFC aerogels. The wood‐derived CNF aerogels exhibit excellent electrical conductivity, a large surface area, and potential as a binder‐free electrode material for supercapacitors. The results suggest great promise in developing new families of carbon aerogels based on the controlled pyrolysis of economical and sustainable nanostructured precursors.     

Nitroxyl‐Radical‐Catalyzed Oxidative Coupling of Amides with Silylated Nucleophiles through N‐Halogenation

A nitroxyl‐radical‐catalyzed oxidative coupling reaction between amines with an N‐protecting electron‐withdrawing group (EWG) and silylated nucleophiles was developed to furnish coupling products in high yields, thus opening up new frontiers in organocatalyzed reactions. This reaction proceeded through the activation of N‐halogenated amides by a nitroxyl‐radical catalyst, followed by carbon–carbon coupling with silylated nucleophiles. Studies of the reaction mechanism indicated that the nitroxyl radical activates N‐halogenated amides, which are generated from N‐EWG‐protected amides and a halogenation reagent, to give the corresponding imines.     

Biphenyl‐Derived Phosphepines as Chiral Nucleophilic Catalysts: Enantioselective [4+1] Annulations To Form Functionalized Cyclopentenes

Because of the frequent occurrence of cyclopentane subunits in bioactive compounds, the development of efficient catalytic asymmetric methods for their synthesis is an important objective. Introduced herein is a new family of chiral nucleophilic catalysts, biphenyl‐derived phosphepines, and we apply them to an enantioselective variant of a useful [4+1] annulation. A range of one‐carbon coupling partners can be employed, thereby generating cyclopentenes which bear a fully substituted stereocenter [either all‐carbon or heteroatom‐substituted (sulfur and phosphorus)]. Stereocenters at the other four positions of the cyclopentane ring can also be introduced with good stereoselectivity. An initial mechanistic study indicates that phosphine addition to the electrophilic four‐carbon coupling partner is not the turnover‐limiting step of the catalytic cycle.