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Here a Cu(I)/Cu(III)/Cu(II)/Cu(III)/Cu(I) redox sequence is revealed in copper-catalysed aryl iodide coupling, capturing intermediate species and redefining the mechanistic understanding of the reaction.

Single molecular machines are capable of a variety of functions, but methods to couple motion between them are still lacking. Here, Wasioet al. report the emergent behaviour of spontaneously formed two-dimensional crystals, which display correlated switching of their sub-molecular rotor units.

Understanding molecule-surface interactions is key to neat on-surface synthesis of functional nanomaterials. Here, the authors measure interactions of metal surface atoms with CO-terminated tips to reveal their nature and reliable adsorption sites.

Monomeric N-heterocyclic carbenes (NHCs) can act as molecular modifiers of metal surfaces and thus affect heterogeneous catalytic behaviour. Now NHC polymers have been formed on gold surfaces, consisting of ballbot-type repeating units bound to single gold adatoms. Conformational, electronic and charge transport properties explain the high surface mobility of the incommensurate NHC polymers.

Graphene nanoribbons are potential systems for engineering topological phases of matter, but the pre-required gapped phases are difficult to find. Here, the authors show that chiral graphene nanoribbons undergo a transition from metallic to topological insulators, and then to trivial band insulators as they are narrowed down to nanometer widths.

The P2X4 receptor, an ATP-activated ion channel, plays a role in chronic pain, inflammation, and cancer. Authors in this work discover an extracellular allosteric binding site that interacts with anthraquinone derivatives, and is narrowed by ionic lock formation.

Optimized Ullmann coupling reaction of heterotriangulene precursors allows the synthesis of two-dimensional π-conjugated polymers with ordered domains larger than 100 × 100 nm² showing both Dirac cones and flat bands in their electronic structure.

π-magnetism in graphene systems has been predicted but remains an experimental challenge. Here the authors report the discovery of unpaired electron spins localized in certain sites of graphene nanoribbons, and the measurement of their coupling by inducing singlet-triplet excitations with a scanning tunneling microscope.

The on-surface synthesis of graphene nanoribbons typically relies on Ullmann polymerization followed by an internal cyclodehydrogenation. Here, following these two steps, the authors expand the synthetic protocol by adding controlled phenyl migration and intraribbon aryl-aryl dehydrogenative coupling to afford graphene nanoribbons with periodic arrays of [18]annulene pores at the edges.

On-surface synthesis is a useful approach for the construction of nanoporous graphene materials, which are in turn of interest for various electronic applications. Here, the authors review the latest developments in the on-surface synthesis of atomically precise pristine and hetero-atom doped nanoporous graphene materials.

On-surface synthesis of nanographenes proceeds differently on metals than on semiconductors or insulating substrates. Here, the authors perform substrate type-independent chemistry with atomic hydrogen acting as a catalyst in the intramolecular cyclodehydrogenation reaction of polyarenes, yielding atomically precise nanographenes.

A safe, versatile deaminative method converts aromatic amines into diverse C–X and C–C bonds via N-nitroamine intermediates, enabling broad one-pot cross-couplings without hazardous diazonium salts.

Heterogeneous geminal-atom catalysts, which pair single-atom sites in specific coordination and spatial proximity, offer a new avenue for the sustainable manufacture of fine chemicals.

This Review describes recent work where scanning probe techniques are used to effect the formation and cleavage of chemical bonds. We contextualize this progress in terms of single-molecule manipulation and summarize implications for synthetic chemistry and future studies.

New studies that document the effect of polymetallic nodule mining vehicles on deep-sea biodiversity suggest that keeping up with technological innovations will be key to more realistic impact assessments of deep-sea mining.

Graphene nanoribbons with zigzag edges are key candidates for spintronic applications due to their tunable bandgaps and spin-polarized edge states. Now it has been shown that hybrid ribbons embedded with metalloporphyrins enable strong electronic and magnetic coupling between distant metal centres, positioning such hybrids as promising materials for quantum devices.

Controlling the regioselectivity in the coupling of simple aromatics is challenging. Now, para–para selectivity is achieved during the aerobic dehydrogenative homocoupling of arenes through a shape-selective catalyst based on molecular palladium confined within the framework of zeolite materials.

Precise control of charge and spin states in quantum dots is often challenging. Here, the authors show systematic manipulation of the electron occupation in graphene nanoribbons laying on MgO.

Peptide stapling is a powerful technique used to lock peptide conformations and modulate peptide functions. This Review highlights the newest development in non-symmetric stapling of native peptides bearing natural amino acids, elucidating current advances, challenges and future opportunities.

Hydrogen borrowing is an attractive method for C-N bond formation - avoiding multiple alkylation products and reducing waste - but often is carried out with noble metals. Here the authors show that a manganese catalyst allows the selective N-alkylation of amines with alcohols.

A dual cobalt and photocatalysis system provides a way to assemble anilines from cyclohexanones and amines by progressively dehydrating the intermediate imine.

Molecular tessellations of complex tilings are difficult to design and construct. Here, the authors show that molecular tessellations can be formed from a single building block that gives rise to two distinct supramolecular phases, whose self-similar subdomains serve as tiles in the periodic tessellations.

Understanding cycloaddition mechanisms is beneficial for the creation of extended carbon nanostructures, yet traditional models often overlook symmetry-based mechanistic effects. Here, the authors employ topological classifiers to identify symmetry-forbidden pathways in polycyclic aromatic azomethine ylide cycloadditions, revealing that topologically-allowed endothermic reactions can guide nanographene engineering.

Graphene nanostructures with π magnetism offer a chemically tunable platform to explore correlated magnetic interactions. Here, the on-surface synthesis of spin-1/2 antiferromagnetic Heisenberg chains based on N-doped nanographene units is reported. The spin chains are synthesized through ortho sp³ C–H activated polymerization and exhibit parity-dependent magnetic ground states.

Scanning tunneling microscopy is a powerful tool for determining the electronic structure of surface adsorbates. Here, carbon monoxide functionalized tips enable more accurate probing of the molecular states of graphene nanorings adsorbed on a gold surface.

Porous framework material DUT-49 was recently demonstrated to exhibit a unique counterintuitive negative gas adsorption (NGA) behaviour. Here the authors identify framework DUT-50 as an additional pressure amplifying material that features distinct NGA transitions, and suggest structural design criteria to access other such materials.

The preparation of high quality crystalline covalent organic framework (COF) films without polymer contamination and controllable thickness is desirable for optoelectronic applications. Here, the authors report a diffusion-limited synthesis strategy for wafer-scale COF films with a controlled structure, thickness, patterning, and crystallization degree based on the adjustment of the precursor building block films.

Research into the control of conformational arrangements is of great importance for achieving bespoke nanoarchitectures. Here, the authors achieve topology selectivity of a conformationally flexible precursor by Se doping.

Helium is an atom of great scientific interest, yet much debate exists surrounding the shape its molecules form. Here Voigtsberger et al. present experimental results imaging the wavefuction of ⁴He₃ and ³He₄He₂ trimer systems, which suggest that ⁴He₃ is a random cloud while ³He₄He₂is a quantum halo state.

Zig-Zag graphene nanoribbons have edge states that are predicted to be spin-polarized, however, measurement of these spin-polarized states has proved elusive. Here, Brede et al overcome this challenge by growing graphene nanoribbons on ferromagnetic GdAu2, allowing for the direct observation of the spin-polarized edge states.

In wildlife tagging, stress from capture and handling can alter post- release behavior and potentially study interpretations. This study of 42 mammal species shows that these effects diminish within 4–7 days, and quicker for animals in high human activity areas indicating adaptation to disturbance.

Direct radical C–H amination strategies have exhibited innovation, but challenges remain with C–H amination of electron-poor nitroarenes due to the essence of the electron-deficient nitrogen radical. Herein, the authors report a transition metal-free dehydrogenative C(sp²)-H/N-H cross-coupling between electron-poor nitroarenes and amines.

The synthesis of topological molecular carbons with persistent chirality is challenging. Here, a triply twisted Möbius carbon nanobelt was synthesized and its two enantiomers were isolated, showing a large absorption dissymmetry factor.

Catalysed oxidative C-C bond formation reactions are important in the synthesis of natural products, but poorly tolerated by polyphenolic flavones. Here the authors report the reactivity of molecular oxygen in alkaline water without added catalyst for the synthesis of a collection of flavone dimers and trimers.

On-surface dehydrogenative bond formation between sp³-hybridized carbon atoms usually requires high temperatures. Now, it has been shown that the higher homologue, silicon, can undergo dehydrogenative polymerization at room temperature on metal surfaces. This process creates well-ordered structures on Au(111) and Cu(111), with different stereoselectivity depending on the metal.

Forming 2D polymers in a controlled manner on the atomic and molecular level is difficult. Here, Feng and others have used Schiff-base polycondensation reactions at an air-water or liquid-liquid interface to form porphyrin containing monolayer and multilayer 2D polymers.