The new iron age: The stabilization of an iron(III) complex with mesoionic carbenes has been shown to lead to record-breaking excited-state lifetimes and an unprecedented spin-allowed radiative decay from a ²LMCT state. These results set the stage for a sustainable future in the new “iron age”.

We shall overcome: As a result of efforts to overcome the sensitivity challenge of liquid-state NMR spectroscopy, a thousand-fold signal enhancement was achieved by dynamic nuclear polarization (DNP) for ¹³C signals at high magnetic field (3.4 T) and room temperature, thereby exceeding the predicted limitations of high-field liquid-state in situ DNP.

Twisted system: A photochemical cyclodehydrochlorination (CDHC) reaction is a relatively mild and efficient way to access highly contorted, helically coiled graphene nanoribbons. The material is characterized by a number of techniques and boasts a relatively large optical band gap of 2.15 eV.

The ability of nickel to cleave strong σ-bonds is again in the spotlight after a recent report that demonstrates the feasibility of using nickel complexes to promote decarbonylation of diaryl ketones. This transformation involves the cleavage of two strong C−C(O) bonds and avoids the use of noble metals, hence reinforcing the potential of decarbonylation as a technique for forging C−C bonds.

Cyclic versus linear: The superiority of cyclic polymers over their linear counterparts is highlighted. Cyclic poly(2-oxazoline)s have been shown to provide excellent shielding properties when grafted to TiO₂ surfaces and Fe₃O₄ nanoparticles owing to their ultrahigh grafting densities leading to low friction surfaces, superior antifouling properties, and extreme nanoparticle stabilization.

Sunburned: Visible light facilitates the acceptorless dehydrogenation of saturated hetero- and carbocycles with an annulated benzene ring (see scheme; X=N and CH₂). These aromatizations occur at room temperature. The new methods are not only useful for the synthesis of bicyclic heteroarenes and arenes with diverse substitution patterns but also potentially attractive for hydrogen-storage materials.

Breaking the mirror (plane): A palladium-catalyzed desymmetrization strategy via β C−H activation provides an alternate approach for solving the age-old challenge of introducing an α-methyl stereocenter to a molecule.

Hydronium ions have been reversibly stored for the first time in an electrode of crystalline 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA). A highly reversible discharge–charge behavior of PTCDA was observed in an aqueous acidic electrolyte of 1 m H₂SO₄. The capacity and the operation potentials are comparable to that of Na-ion storage in the same electrode.

Go Aggies! Go Chemikers! The word “gig” applies to a multipronged metal tool for hunting frogs and fish. It constitutes part of a rallying cry, “gig ’em” that inspires Texas A&M Aggies to victory in athletic and academic competitions. This Highlight examines recent victories in the C C cleavage of benzene made possible by a four-pronged iridium gig that yields a “spring-loaded” norbornadiene-like structure with significant ring strain.

AC line-filtering on-chip micro-supercapacitors (MSCs) based on coordination polymer frameworks were fabricated by a facile layer-by-layer method. The reported on-chip MSCs showed a low impedance phase angle of −73° at 120 Hz and a high power density of up to 1323 W cm⁻³ with a low relaxation time constant of 0.27 ms.

More insight or only more parameters? A recent claim that the development of new density functional theory (DFT) functionals is straying from the right path has sparked a lively discussion among theoretical chemists about the future of DFT.

Green redox flow batteries: The development of environmentally benign sustainable energy storage systems is eagerly awaited. Organic and organometallic-based electroactive materials are green alternatives to realize this goal. Using rational molecular design and function-oriented organic synthesis, a general design principle is presented to build high-performance green redox flow batteries.

A CO surrogate: In two recent studies, CO₂ has not only been applied as a CO source in the hydroformylation of alkenes and the carbonylative Hiyama–Denmark coupling of aryl iodides, but more interestingly it also attenuates or improves the reactivity of the reactants.

When it takes eight to tango: Since the synthesis of the simplest of all knots, the trefoil knot, in 1989, the formation of more complex knots has remained extremely challenging. The synthesis of the most complex molecular knot made to date, the 8₁₉, by Leigh and co-workers thus represents a major step towards building topologically complex architectures.

Modular redefinition: A long-standing paradigm in modular polyketide synthase enzymology, namely the definition of a module, has been challenged by Abe and co-workers in their recent study. With this new understanding has emerged renewed hope for engineering these assembly lines to produce new materials and medicines.

Potential for nitrogenase: Milton, Minteer, and co-workers report the first evidence for the bioelectrochemical reduction of N₂ to ammonia by nitrogenase. This complex enzyme could be wired to an electrode by using the soluble mediator methyl viologen; this very simple approach makes it possible to develop a variety of biotechnological devices.

The cream of the crop: With the world facing a projected shortfall of crops by 2050, new approaches are needed to boost crop yields. Metabolic feeding of plants with photocaged trehalose-6-phosphate (Tre6P) can increase levels of the signaling metabolite Tre6P in the plant. Reprogramming of cellular metabolism by Tre6P stimulates a program of plant growth and enhanced crop yields, while boosting starch content.

Radical chemistry meets NHCs: NHC catalysis and single electron oxidants have been merged in several transformations, allowing the synthesis of useful β-hydroxy esters, cyclopentanones, and spirocyclic γ-lactones in a highly stereoselective manner. The key step is the oxidation of the NHC homoenolate equivalent to a radical species via a single-electron transfer process (see scheme).

Linking two worlds: As a further expansion of the biocatalytic repertoire, carbene insertion into Si−H bonds catalyzed by the heme protein cytochrome c was recently reported. This new biocatalyst holds great promise because it enables the highly selective incorporation of silicon into molecules without prior protection of existing functional groups.

Patch works! Patchy block copolymer micelles with a corona consisting of two chemically different patches have been designed for the selective binding of catalytically active nanoparticles. The fabrication of nonwoven supports by electrospinning was combined with crystallization-driven self-assembly for precise control over micelle formation to prepare a new recyclable catalyst platform.