Advances in Pd-catalysed cross-coupling reactions have facilitated the development of stereospecific variants enabling the use of configurationally stable, enantioenriched, main-group organometallic nucleophiles to form C(sp3)–C(sp2) bonds. Such stereospecific cross-coupling reactions constitute a powerful synthetic approach to attaining precise 3D control of molecular structure, allowing new stereogenic

Carbon–carbon (C–C) bonds make up the skeletons of most organic molecules. The selective manipulation of C–C bonds offers a direct approach to editing molecular scaffolds but remains challenging. The kinetic inertness of C–C bonds can be overcome with transition-metal catalysis, which, nevertheless, relies on a substrate being highly strained or bearing a permanent directing group (DG). The driving

Natural biomolecular systems have evolved to form a rich variety of supramolecular materials and machinery fundamental to cellular function. The assembly of these structures commonly involves interactions between specific molecular building blocks, a strategy that can also be replicated in an artificial setting to prepare functional materials. The self-assembly of synthetic biomimetic peptides thus

First-row transition metal stannyls feature an unusual combination of M–Sn bonding and a high-spin ground state.

Thanks to the development of experimental high-pressure techniques and methods for crystal-structure prediction based on quantum mechanics, in the past decade, numerous new compounds, mostly binary, with atypical compositions have been predicted, and some have been synthesized. Differing from conventional solid-state materials, many of these new compounds are comprised of various homonuclear chemical

Single-molecule conductance measurements enable different conformers of cyclohexane to be observed at room temperature.

Controlling cooperativity, synchronization, amplification and translation of intermolecular and intramolecular dynamics over different length scales for applications in stimuli-responsive robust solids are considered key challenges in materials sciences. In this Perspective, we discuss the possibility of embedding artificial molecular machines into heterogeneous robust frameworks with the goal of creating

Spectroscopy reveals the speciation of a merocyanine photoacid that serves as a light-sensitive pH switch.

The formation of nanobubbles can limit the efficiency of nanoelectrodes. Molecular simulations can provide important physical insights on the nanobubble nucleation process that results in the current insensitivity to applied potential.

Two templates can stack together to enable the formation of a large macrocycle, providing they bind cooperatively to the target. The approach may enable the synthesis of very large macrocycles using relatively simple templates.

The fast and non-adiabatic nature of photoinduced isomerization reactions makes it difficult to pin down their mechanisms. Time-resolved photoelectron spectroscopy using high energy photons and simulations can elucidate the mechanism of the ultrafast ring opening of thiophenone molecules in the gas phase.

As the world erupts with demands for racial justice, the chemistry community has the obligation, opportunity and momentum to drive for diversity and inclusion in the sciences. Efforts towards that end must begin by allocating opportunities for success on the basis of potential, not privilege, and follow through by soliciting and acting upon feedback from the scholars we have recruited. As the world

A new diradical features two three-electron sigma interactions between pairs of Se atoms.

Nature uses multinuclear metal clusters to catalyse a number of important multielectron redox reactions. Examples that employ complex Fe–S clusters in catalysis include the Fe–Mo cofactor (FeMoco) of nitrogenase and its V and all-Fe variants, and the [FeFe] and [NiFe] hydrogenases. This Perspective begins with a focus on the catalytic H-cluster of [FeFe] hydrogenase, which is highly active in producing

Amino acid homorepeats, or homorepeats, are polypeptide segments found in proteins that contain stretches of identical amino acid residues. Although abnormal homorepeat expansions are linked to pathologies such as neurodegenerative diseases, homorepeats are prevalent in eukaryotic proteomes, suggesting that they are important for normal physiology. In this Review, we discuss recent advances in our

Bioorthogonal chemistries enable researchers to interrogate biomolecules in living systems. These reactions are highly selective and biocompatible, and can be performed in many complex environments. However, like any organic transformation, there is no perfect bioorthogonal reaction. Choosing the ‘best fit’ for a desired application is crucial. Correspondingly, there must be a variety of chemistries

This Review aims to critically analyse the emerging field of chemical reactivity at aqueous interfaces. The subject has evolved rapidly since the discovery of the so-called ‘on-water catalysis’, alluding to the dramatic acceleration of reactions at the surface of water or at its interface with hydrophobic media. We review critical experimental studies in the fields of atmospheric and synthetic organic

Protein–RNA interactions have crucial roles in various cellular activities, which, when dysregulated, can lead to a range of human diseases. The identification of small molecules that target the interaction between RNA-binding proteins (RBPs) and RNA is progressing rapidly and represents a novel strategy for the discovery of chemical probes that facilitate understanding of the cellular functions of

Molecular transition-metal–ligand complexes are emerging as useful paradigms in materials science. Transition metal complexes have diverse metal d electron configurations, oxidation states, coordination numbers and geometries such that they can undergo a diverse array of electronic transitions. Metal-to-ligand charge-transfer transitions and their associated excited states are especially attractive

Vibronic coherences can guide a synthetic control of the lifetime of the excited states in iron(ii)-based complexes.

Experimental models show that through-space effects dominate over through-bond effects when considering the influence of so-called electron-withdrawing or electron-donating substituents on molecular conformation and reactivity.

The power of chemistry to prepare new molecules and materials has driven the quest for new approaches to solve problems having global societal impact, such as in renewable energy, healthcare and information science. In the latter case, the intrinsic quantum nature of the electronic, nuclear and spin degrees of freedom in molecules offers intriguing new possibilities to advance the emerging field of

High-valent metal–oxo species with multiply-bonded M–O groups have been proposed as key intermediates in many biological and abiological catalytic oxidation reactions. These intermediates are implicated as active oxidants in alkane hydroxylation, olefin epoxidation and other oxidation reactions. For example, [FeivO(porphyrinato•−)]+ cofactors bearing π-radical porphyrinato•− ligands oxidize organic

The process by which chemistry can give rise to biology remains one of the biggest mysteries in contemporary science. The de novo synthesis and origin of life both require the functional integration of three key characteristics — replication, metabolism and compartmentalization — into a system that is maintained out of equilibrium and is capable of open-ended Darwinian evolution. This Review takes

Mendeleev’s introduction of the periodic table of elements is one of the most important milestones in the history of chemistry, as it brought order into the known chemical and physical behaviour of the elements. The periodic table can be seen as parallel to the Standard Model in particle physics, in which the elementary particles known today can be ordered according to their intrinsic properties. The

Abiotic sources of H2 in the lithosphere outweigh the sinks, with the balance potentially being available to a large microbial community.

Although they are generally poor coupling agents under palladium catalysis, germanes are easily cross-coupled under gold catalysis, enabling a new orthogonal cross-coupling reaction.

Rational design of compounds with specific properties requires understanding and fast evaluation of molecular properties throughout chemical compound space — the huge set of all potentially stable molecules. Recent advances in combining quantum-mechanical calculations with machine learning provide powerful tools for exploring wide swathes of chemical compound space. We present our perspective on this

Despite their similarity with surfactants, the mechanism by which hydrotropes assist in solubilizing apolar molecules in water is not totally understood. A mechanism is now proposed that identifies apolar interactions as driving forces of hydrotropy, in agreement with a statistical thermodynamic picture.

Enzymes exercise impeccable control over chemoselectivity, site selectivity and stereoselectivity in reactions they mediate, such that we have witnessed a surge in the development of new biocatalytic methods. Although carbon–carbon (C–C) bonds are the central framework of organic molecules, biocatalytic methods for their formation have largely been limited to a select few lyase enzymes. Thus, despite

One can combine two distinct chain-transfer agents to tune the dispersity of vinyl polymers. The polymer chains remain living and can be transformed into diblock copolymers.

A central feature of most lignocellulosic-biomass-valorization strategies is the depolymerization of all its three major constituents: cellulose and hemicellulose to simple sugars, and lignin to phenolic monomers. However, reactive intermediates, generally resulting from dehydration reactions, can participate in undesirable condensation pathways during biomass deconstruction, which have posed fundamental

An unexpected epoxide deoxygenation reaction was observed to occur with inversion of stereochemistry and has enabled development of a method for alkene isomerization.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Fluorophores have transformed the way we study biological systems, enabling non-invasive studies in cells and intact organisms, which increase our understanding of complex processes at the molecular level. Fluorescent amino acids have become an essential chemical tool because they can be used to construct fluorescent macromolecules, such as peptides and proteins, without disrupting their native biomolecular

Sample preparation and instrumentation for macromolecular mass spectrometry continue to evolve, making the technique more relevant than ever.

Uncharged polymers on the surface of charged colloidal particles can help to control their self-assembly into ordered structures.

Helices are the most prevalent secondary structure in biomolecules and play vital roles in their activity. Chemists have been fascinated with mimicking this molecular conformation with synthetic materials. Research has now been devoted to the synthesis and characterization of helical materials, and to understand the design principles behind this molecular architecture. In parallel, work has been done

A persistent silylene complex of CO is reminiscent of metal carbonyls and features interesting bonding interactions.

A new book by Peter Wothers delves into the tumultuous history of naming (and symbolizing) the elements.

An autobiography by Martin Karplus, from his childhood and continuing right through to a journey to Stockholm to receive the 2013 Nobel prize.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

A hollow multishell structure (HoMS) is an assembly of multiple shells with voids between the individual shells. Accessible through nanopores, these voids represent separate reaction environments in the same assembly, such that HoMSs have unique properties that are applicable to diverse fields. These applications have mostly exploited the large specific surface area, high loading capacity and/or buffering