Correction for ‘Voltage issue of aqueous rechargeable metal-ion batteries’ by Zhuoxin Liu et al., Chem. Soc. Rev., 2020, DOI: 10.1039/c9cs00131j.

Correction for ‘The challenges of glycan recognition with natural and artificial receptors’ by Stefano Tommasone et al., Chem. Soc. Rev., 2019, 48, 5488–5505.

Correction for ‘Solid-state electrical applications of protein and peptide based nanomaterials’ by Sayak Subhra Panda et al., Chem. Soc. Rev., 2018, 47, 3640–3658.

The autoxidation of organic materials is a detrimental radical chain process often leading to their rapid deterioration unless they are protected by preventive and/or chain breaking antioxidants. The properties of the more important family of the latter ones, that one of phenols, are illustrated in this tutorial review. A short outline of diarylamine antioxidants is also given. We describe simple experimental methods employed for the determination of the two parameters more useful for estimating the inhibiting power of antioxidants, that is the kinetic rate constant for their reaction with the chain carrying peroxyl radicals, k(inh), to give persistent phenoxyl or aminyl radicals and the bond dissociation enthalpy BDE(X-H) (X = O, N) of the bond cleaved in the inhibition process. The dependence of these parameters on the number and nature of the substituents is discussed and, in the case of phenols, a simple rule allowing to predict with reasonable accuracy the BDE and k(inh) values, from their structure. The effect of solvent polarity on the antioxidant power is also described. Finally, the information on the mechanism of reaction between phenols and peroxyl radicals provided by both experiments and theoretical calculations are examined. Because of difficulties associated with the analysis of non-homogenous systems all the reported results refer to homogenous solution in which experimental data can be analysed by means of more reliable and complete treatments.

Bioorthogonal chemical reactions are paving the way for new innovations in biology. These reactions possess extreme selectivity and biocompatibility, such that their participating reagents can form covalent bonds within richly functionalized biological systems--in some cases, living organisms. This tutorial review will summarize the history of this emerging field, as well as recent progress in the development and application of bioorthogonal copper-free click cycloaddition reactions.

This tutorial review discusses the immobilization of alkyne-terminated cytochrome c oxidase models on azide-functionalized self-assembled monolayers (SAM) coated gold electrodes that was made possible by click chemistry. The rate of electron delivery from the electrode to the model could be tuned by changing the nature of the SAM. Biologically relevant electron transfer rates (2-4 s(-1)) were obtained on slow SAMs allowing the model to turn over catalytically under steady-state conditions. Hence, click chemistry was a crucial tool to demonstrate, through electrocatalytic studies: (1) the role played by several features present in the distal side of the model, such as the Cu(B)-Tyr244 pair, the distal pocket, and the stabilizing role of a distal water cluster; (2) the reversible inhibition of O(2) reduction by H(2)S.

The supramolecular chemistry of anions provides a means to sense and manipulate anions in their many chemical and biological roles. For this purpose, Click chemistry facilitated the synthetic creation of new receptors and thus, an opportunity to aid in the recent re-examination of CH...anion hydrogen bonding. This tutorial review will focus on the privileged C-H hydrogen bond donor of the 1,2,3-triazole ring systems as elucidated from anion-binding studies with macrocyclic triazolophanes and other receptors. Triazolophanes are shape-persistent and planar macrocycles that direct four triazole and four phenylene CH groups into a 3.7 A cavity. They display strong (log K(Cl(-)) = 7), size-dependent halide binding (Cl(-) > Br(-) >> F(-) >> I(-)) and a rich set of binding equilibria. For instance, the too large iodide (4.4 A) can be sandwiched between two pyridyl-based triazolophanes with extreme positive cooperativity. Computational studies verify the triazole's hydrogen bond strength indicating it approaches the traditional NH donors from pyrrole. These examples, those of transport, sensing (e.g., ion-selective electrodes), templation, and versatile synthesis herald the use of triazoles in anion-receptor chemistry.

The semi-pinacol rearrangement is fast becoming an extremely reliable reaction in organic synthesis allowing the rapid construction of relatively complex stereodefined products in high yield. Recent advances in asymmetric synthesis have also enabled enantiopure precursors to partake in the rearrangement showing that extremely high levels of stereospecificity are observed. In this critical review recent advances in the semi-pinacol rearrangement over the past 15 years are examined which demonstrate the extremely high utility of this reaction towards the development of structurally diverse organic building blocks (74 references).

This critical review aims at presenting recent developments in intramolecular aromatic homolytic substitution which has become one of the common methodologies in modern synthesis. The application of Bu3SnH-mediated cyclisations have proved especially useful. The critical review illustrates the mechanistic considerations required for planning synthetic applications and a wide range of synthetic protocols and natural product syntheses are shown. The latest evidence for the mechanisms involved in aromatic homolytic substitution are presented. (152 references).

The utilization of plant oil renewable resources as raw materials for monomers and polymers is discussed and reviewed. In an age of increasing oil prices, global warming and other environmental problems (e.g. waste) the change from fossil feedstock to renewable resources can considerably contribute to a sustainable development in the future. Especially plant derived fats and oils bear a large potential for the substitution of currently used petrochemicals, since monomers, fine chemicals and polymers can be derived from these resources in a straightforward fashion. The synthesis of monomers as well as polymers from plant fats and oils has already found some industrial application and recent developments in this field offer promising new opportunities, as is shown within this contribution. (138 references.)

This critical review deals with the chemistry and applications of metal alkanoates with medium size (C5 to C12) carbon chain length. A particular emphasis is given to metal 2-ethylhexanoates, which find wide applications as metal-organic precursors in materials science, as catalysts for ring opening polymerizations and also in painting industries for their properties as driers. After a brief introduction and an overview of synthesis, structural and physico-chemical properties, this article discuses extensively the applications of these compounds in materials science. Finally, it identifies and signifies the areas for future research in the looking ahead section. The aim of this review is to bridge the areas of precursor's chemistry and materials science by providing a reference text for researchers working either in or at the interface of these two areas (125 references).

This tutorial review devoted to ligand chemistry deals with the design and properties of ferrocenyl polyphosphines, an original class of multidentate ligands. The development of a varied library of ferrocenyl tetra-, tri- and diphosphine ligands is reviewed. The multidentate nature of these species has led to unique spectroscopic and catalytic properties, in which the spatial proximity of phosphorus atoms is crucial. Regarding their catalytic applications, the key issues of catalyst longevity and ultralow catalyst loadings are discussed. Another part is concerned with fundamental advances gained in physical chemistry for structure elucidation by the study of the intriguing "through-space" NMR spin-spin J couplings existing within several of these polyphosphines.

This tutorial review highlights some active areas of research into non-oxide sol-gel chemistry. These aim to capture some of the advantages of methods developed mainly with oxides for a new generation of functional materials based on main group and metal nitrides, and semiconducting chalcogenides. Sol-gel processing has a long track record in producing useful materials for optical, magnetic, electrical, catalytic and structural applications. Controlled morphologies can be produced on all lengths scales, from ordered mesoporous arrays to thin films, fibres and monoliths. Hence there is an opportunity to produce new morphologies in non-oxides and hence new applications of these materials.

Since the discovery of a stable "bottleable" N-heterocyclic carbene (NHC), there has been a spectacular explosion of interest in this ligand class. This interest stems from a desire to understand the fundamentals of the structure and bonding of these systems, but also because of their numerous and emerging applications in small molecule activation, homogeneous catalysis and Lewis acid-catalysed reactions. In this Tutorial Review, we introduce the reader to NHCs, cover general synthetic methods to prepare anionic tethered NHCs and their metal complexes, and discuss emerging applications in reactivity and catalytic studies.

In recent years, the margin of interaction between computational chemistry and most branches of experimental chemistry has increased at a fast pace. The experimental characterization of new systems relies on computational methods for the rationalization of structural, energetic, electronic and dynamical features. In particular, novel computational approaches allow accurate estimates of molecular parameters from spectroscopic optical observables, giving rise to synergic interactions between experimentalists and theoretically-oriented chemists. Our main objective in this tutorial review is to delineate the degree of advancement of possible integrated computational approaches to the interpretation of optical spectroscopies, with an accent on large molecules in solvated environments, based on the combination of advanced quantum mechanical treatments and stochastic modelling of relaxation processes.

The imine bond--formed by the reversible condensation of an amine and an aldehyde--and its applications as a dynamic covalent bond in the template-directed synthesis of molecular compounds, will be the focus of this tutorial review. Template-directed synthesis--or expressed another way, supramolecular assistance to covalent synthesis--relies on the use of reversible noncovalent bonding interactions between molecular building blocks in order to preorganise them into a certain relative geometry as a prelude to covalent bond formation to afford the thermodynamically preferred product. The use of this so-called dynamic covalent chemistry (DCC) in templated reactions allows for an additional amount of reversibility, further eliminating potential kinetic products by allowing the covalent bonds that are formed during the template-directed reaction to be 'proofread for errors', thus making it possible for the reaction to search out its thermodynamic minimum. The marriage of template-directed synthesis with DCC has allowed chemists to construct an increasingly complex collection of compounds from relatively simple precursors. This new paradigm in organic synthesis requires that each individual piece in the molecular self-assembly process is preprogrammed so that the multiple recognition events expressed between the pieces are optimised in a highly cooperative manner in the desired product. It offers an extremely simple way of making complex mechanically interlocked compounds--e.g., catenanes, rotaxanes, suitanes, Borromean rings and Solomon knots--from relatively simple precursors.

The enantioselective synthesis of C-C bonds is often the pivotal step of a synthesis. Nature has made a variety of versatile enzymes available that catalyse this type of reaction very selectively under mild conditions. Cyanohydrins, acyloins (alpha-hydroxy ketones), alpha-hydroxy acids and aldols (beta-hydroxy ketones) are very efficiently synthesised enantioselectively with the aid of C-C bond forming enzymes, which we discuss in this tutorial review. In the case of the alpha-hydroxy acids the applications of nitrilases in a synthetic dkr even allows a disconnection that has no enantioselective chemical equivalent.

Phthalocyanines (Pcs) offer a high architectural flexibility in structure, which facilitates the tailoring of their physical, optoelectronic and chemical parameters over a very broad range. This tutorial review describes the recent advances in the synthesis of soluble axially substituted or bridged gallium phthalo- and naphthalocyanine compounds, and their photophysical and nonlinear optical properties. The exploitation of the chemical reactivity of the Ga-Cl bond can allow the preparation of a series of highly soluble axially substituted and bridged Pc complexes. Axial substituents in Pcs influence favourably nonlinear optical absorption for the presence of a dipole moment perpendicular to the macrocycle in the axially substituted phthalocyanines. All Z-scans performed exhibit a decrease of transmittance about the focus typical of an induced positive nonlinear absorption of incident light. Substitution and dimerization of the phthalocyanine monomer resulted in significant reductions in the saturation energy density of the material displaying clear evidence of the usefulness of structurally modifying the gallium phthalocyanine unit. Similar to indium phthalocyanines, gallium phthalocyanines are also among the most promising materials that have been investigated as limiters of intense light and the current series presents a selection of structural modifications useful for varying their nonlinear optical properties.

1,3-dipolar cycloaddition reactions of nitrones with alkenes and alkynes are well-studied reactions in solution-phase organic chemistry. However, the number of studies concerned with their application in solid-phase organic synthesis is rather low compared to other 1,3-dipoles, e.g. azides or nitrile oxides. This tutorial review aims to summarise the main approaches towards the application of nitrones in 1,3-dipolar cycloaddition reactions on solid supports in addition to subsequent transformations with polymer-bound isoxazolidines and reactions using polymer-bound catalysts.

Naturally occurring metalloproteins contain metal ions either to introduce a special reactivity or to stabilize a peptide structure. Since the early 1990s, chemists have been trying to use metal coordination for the fixation of short artificial peptides in well-defined cyclic structures. In this tutorial review a survey of the general approaches towards metallacyclopeptides as small cyclic peptide derivatives or as a part of a bigger alpha-helix (or beta-sheet) structure is given. In three case studies it is shown how naturally occurring compounds can be mimicked by metal coordination to non-natural peptide derivatives.

This tutorial review covers recent contributions in the area of linear pi-conjugated systems bound to fullerenes in view of their application as active materials in photovoltaic devices. The first part discusses the concepts of double-cable polymer and molecular hetero-junction and presents several examples of chemically or electrochemically synthesized C60-derivatized conjugated polymers. The second and main part of the article concerns the various classes of C60-derivatized pi-conjugated oligomers designed in view of their utilization in single-component photovoltaic devices. Thus, C60-containing pi-conjugated systems such as oligoarylenevinylenes, oligoaryleneethynylenes and oligothiophenes are discussed on the basis of the relationships between molecular structure, photophysical properties and performances of the derived photovoltaic devices. A brief last section presents some recent examples of surface-attached molecular hetero-junctions based on self-assembled monolayers and discusses possible routes for future research.

Chemical genetics is the study of biological systems using small molecule ('chemical') intervention, instead of only genetic intervention. Cell-permeable and selective small molecules can be used to perturb protein function rapidly, reversibly and conditionally with temporal and quantitative control in any biological system. This tutorial review has been written to introduce this emerging field to a broad audience and focuses later on areas of biology where either it has made a significant impact, or it has the potential to do so: signalling, cytoskeleton, development, protein-protein interactions and gene transcription.

Transition metal (TM) hydrides display a remarkable range of bonding types, encompassing classical M-H moieties, dihydrogen complexes containing the eta 2-H2 ligand, and trihydrides which display quantum mechanical site exchange. Furthermore, C-H, Si-H and B-H moieties can bind to TM centres in an eta 2-manner, to give sigma-bond complexes with a spectrum of M...H contributions. In addition to these primary bonding modes, TM complexes also indulge in a wide spectrum of hydrogen-bonding interactions, including both M...H-X and the unique type M-H...H-X. This review begins with a historical perspective of the development of TM hydride chemistry, and proceeds to focus on three significant developments of the past two decades: the discovery of sigma-bond and dihydrogen complexes, the involvement of TM hydrides in hydrogen bonding, and the role played by quantum mechanical phenomena in the chemistry and dynamics of TM hydrides. The account concludes with an overview of the inter-relationship between these apparently disparate novel aspects of TM hydride chemistry.