Themed collection Celebrating the 2017 RSC Prize and Award Winners

The wide-ranging properties of metal organic frameworks (MOFs) rely in many cases on the presence of defects within their structures and the disorder that is inevitably associated with such defects.

Gold has seen a remarkable transformation from inert noble metal to highly reactive catalyst. However, its organometallic chemistry contains many unknowns. How certain can we be about the species involved in catalytic cycles? This Perspective summarises recent discoveries.

This Perspective discusses target parameters for the electroreduction of CO₂, based on its comparison with water splitting, which is to become a practical alternative for energy storage into fuels and chemicals.

The solution-phase self-assembly or “polymerization” of discrete colloidal building blocks, such as “patchy” nanoparticles and multicompartment micelles, is attracting growing attention with respect to the creation of complex hierarchical materials.

This feature article discusses the range of stereospecific transformations available to enantioenriched boronic esters, and their applications in synthesis.

Here we survey and organise the state-of-the-art understanding of the TM–H–M linkage (M = Mg, Zn, Al, Ga). We discuss the structure and bonding in these complexes, their known reactivity, and their largely unrealised potential in catalysis.

This feature article discusses the rational control of nano-scale metal catalysts for catalytic biomass transformation.

This feature article showcases the use of pyridynes and indolynes to construct functionalized heterocycles and complex natural products.

Gram-negative bacteria are a rich and underexplored source of antibiotics that are assembled via remarkably diverse biosynthetic pathways.

Artificial molecular motors take inspiration from motor proteins, nature's solution for achieving directional molecular level motion. An overview is given of the principal designs of artificial molecular motors and their modes of operation. We identify some key challenges remaining in the field.

The synthesis of biaryls from benzyne intermediates offers an alternative strategy to conventional metal-catalyzed cross-coupling approaches.

This comprehensive review covers polyferrocenylsilanes (PFSs), a well-established, readily accessible class of main chain organosilicon metallopolymer. The focus is on the recent advances involving PFS homopolymers and block copolymers and the article covers the synthesis, properties, and applications of these fascinating materials.

This review discusses the origins, latest advances, challenges, and future directions of the emerging field of ultrafast surface-enhanced Raman spectroscopy.

Biofluid vibrational spectroscopy, a promising tool for rapid disease diagnosis.

Genetic variants in haem metabolism enzymes can be predisposition factors for adverse reactions in some individuals. New areas of haem biology may also be associated with idiosyncratic effects which are yet to be identified.

This review describes progress in the field of artificial switchable catalysts, where the rate acceleration, stereochemistry and/or chemoselectivity of catalysed processes can be switched through external stimuli.

Wavelength-selective deprotection is an attractive method to control multiple functions in one system using light.

This review takes a fresh approach from the patient perspective; offering insight into the applications of midinfrared biomedical spectroscopy.

Food allergy is an increasing problem. If we fail to realise the promise of current risk assessment and risk management of food allergens through lack of ability to measure them reproducibly and with traceability to an international unit of measurement, the analytical community will have failed a significant societal challenge.

Major food adulteration and contamination events occur with alarming regularity and are known to be episodic, with the question being not if but when another large-scale food safety/integrity incident will occur.

The strategic and economic benefits of C–H functionalization logic are analyzed through the critical lens of total synthesis.

Surpassing traditional organolithium bases, regioselective magnesiation of N-heterocyclic molecules is accomplished using a Mg base with a β-diketiminate steric stabilizer.

The average emission angle and information depth of a photoelectron spectroscopy experiment that employs a liquid microjet is determined using SESSA and the predicted photoelectron intensities are compared with those from a flat aqueous interface.

Addition of 2 equiv. of CuI to a [Cu]₄ multimetallic complex results in cluster formation leading to the isolation of a rare bicapped tetrahedral [Cu₆I₂] cluster that is stabilised by two conformationally constrained polynucleating ligands.

Bifunctional transaminases enable a strategy for the production of chiral amines using small excesses of diamine donors.

The array of naphthyl chromophores in a self-assembled cage can effect photoinduced energy- or electron-transfer to guests in the central cavity.

A deeper investigation of the chemistry that occurs on the newly discovered epigenetic DNA bases 5-hydroxymethyl-(hmdC), 5-formyl-(fdC), and 5-carboxy-deoxycytidine (cadC) requires chemical tool compounds, which are able to dissect the different potential reaction pathways in cells.

A dyad of covalently anchored [Ru(diimine)₃]²⁺ and a biotinylated triarylamine for the photogeneration of a charge-separated species within streptavidin.

Immobilization and protection of artificial imine reductase in silica nanoparticles increases its activity and protects from various denaturing stresses.

An industrial-scale method employing a phenylalanine ammonia lyase enzyme.

A light-operated molecular nanodevice is able to transport an acetyl cargo intramolecularly over a distance of about 2 nm.

Simple carbene complexes of copper halides give photoluminescence quantum yields of up to 96%, with sub-nanosecond emission lifetimes.

A unique square planar anionic ruthenium(0) complex with amido and amine donors undergoes rapid NH oxidative addition/elimination reactions.

Water-soluble metal–organic complex array 1, bearing Ru(II), Pt(II) and Rh(III) complexes at the side residues of the short peptide, exhibits anion and pH-responsive self-assembling behaviours in aqueous media.

We show controlled release over a 30 day period compared with the release from crystalline MOF, which occurs in less than 2 days.

The ability to rapidly generate a pair of aptamers that bind independently to a protein target would greatly extend their use as reagents for two site (‘sandwich’) assays.

Biosynthetic incorporation of an azide-proline chemical reporter into collagen allows selective imaging in live foetal ovine osteoblasts using a strain-promoted [3+2] azide–alkyne cycloaddition reaction.

Thiol-ene chemistry under mild conditions is reported using titania as a cheap and user-friendly photoredox catalyst.

Organomagnesium reagents enable swift and versatile derivatisation of diarylimines to the corresponding α-substituted diarylmethylamines in excellent yields, through fast and clean reactions.

Atomized spray deposition of 3,4-ethylenedioxythiophene monomer in the presence of triflic anhydride vapour yields electrically conducting poly(3,4-ethylenedioxythiophene) layers.

Photoinduced electron transfer dynamics are described for a set of dyads comprising rylenediimide anion chromophores and a Re(bpy)(CO)₃ metal center.

A type B radical-SAM methylase homologue catalyses thiazoline C-methylation as the final step of watasemycin biosynthesis in Streptomyces venezuelae ATCC10712.

The use of a weakly coordinating monodentate directing group for copper-mediated ortho-hydroxylation and amination reactions allows for the identification of an external oxazoline ligand as a promoter.

Photodriven charge transfer dynamics are described for an atomic layer deposition-stabilized, organic dye-sensitized photocathode architecture that produces hydrogen.

Polyketide synthase reductive chain release and subsequent transamination are key steps in the biosynthesis of polyketide alkaloids in actinobacteria.

Self-sorting between n-type and p-type gelators results in effective visible-active photoconductive xerogels.

A novel fullerene-bipyridine-Pt-catecholate triad forms the lowest energy charge separated state upon photoexcitation, investigated by time-resolved infrared spectroscopy.

We report the synthesis and characterization of terminal uranium(IV) hydrosulfido and sulfido complexes, supported by the hexadentate, tacn-based ligand (^Ad,MeArO)₃tacn³⁻.

DFT, TAP, and operando PGAA studies demonstrate that the complex and dynamic surface chemistry of hydrogen halide oxidation on rutile-type catalysts determines the activity and stability patterns for halogen production.

The formal cyclopentane-1,3-diyl derivatives [E¹(μ-NTer)₂({E²C} = NDmp)] (Ter = 2,6-dimesityl-phenyl, Dmp = 2,6-dimethylphenyl) were prepared by 1,1-insertion of CNDmp into the N–E² bond of [E¹(μ-NTer)₂E²] (E¹ = N, P; E² = P, As).

Introduction of a biotinylated monophosphine palladium complex within streptavidin affords an enantioselective artificial Suzukiase. Site-directed mutagenesis allowed the optimization of the activity and the enantioselectivity of this artificial metalloenzyme. A variety of atropisomeric biaryls were produced in good yields and up to 90% ee.

Using two alternative methodologies, new light has been shed on the stability and rational formation of abnormal NHC–gallium complexes.

We report the addition of M–H bonds (M = Al, Zn, Mg) to a Rh(III) intermediate generated from the reductive elimination of triethylsilane from [Cp*Rh(H)₂(SiEt₃)₂].

Remote functionalization of hydrocarbons could be achieved through successive zirconocene-mediated allylic C–H bond activations followed by a selective C–C bond cleavage.

Rhodium(III)-catalyzed C–H olefination reaction using air as the sole oxidant.

The direct cross-coupling of alkenyllithium reagents with aryl and alkenyl halides is described. The use of a catalyst comprising Pd₂(dba)₃/XPhos allows for the stereoselective preparation of a wide variety of substituted alkenes in high yields under mild conditions.

The activation mode of a rotaxane-based organocatalyst with both secondary amine and squaramide catalytic units can be switched with acid or base, affording different products from a mixture of three building blocks.

Structural, spectroscopic, and DFT analysis of the first molecular complexes of Th²⁺ indicate they have a 6d² electron configuration of the type expected for the transactinide ions Rf²⁺ and Db³⁺.

The pyrazole and salen ligandosides, when combined, are able to create stable multi-copper ion complexing DNA duplex structures in a cooperative fashion.

The [Tp′Rh(P(OMe)₃)] fragment is investigated for C–H bond activation and bond strength information is compared with that for [Tp′Rh(PMe₃)] and [Tp′Rh(CNneopentyl)] fragments, showing bond energy correlations that follow the order CNneopentyl < P(OMe)₃ < PMe₃.

We report a nitro-aryl fluorogen capable of being enzymatically converted into a bright fluorophore suitable for single-molecule imaging in cells.

A facile, solid-state mechanochemical method was developed for the synthesis of low molecular weight chitosan (LMWC) in one step from chitin and crude shrimp shell powders, in which chitin undergoes simultaneous deacetylation and depolymerisation in the presence of a base catalyst under mechanical milling.

We show the importance of the self-assembly of a perylene bisimide on its photocatalytic activity.

By studying interactions of a range of probes, we can simultaneously study the surface chemical properties of NMR-invisible gel fibres.

The OH radical production from the near-ultraviolet photolysis of peroxy radicals derived from isoprene has been investigated.

A novel cobalt orthosilicate, Na₂CoSiO₄, shows promise as a high voltage (3.3 V vs. Na/Na⁺) cathode material for sodium-ion batteries.

We have used a family of Zr-based metal–organic frameworks (MOFs) with different functionalized (bromo, nitro and amino) and extended linkers for drug delivery.

Columnar shifts are degrees of freedom in molecular perovskites of relevance to phase transitions, improper ferroelectricity, and negative thermal expansion.

In this study, we introduce an optofluidic method for the rapid construction of large-area cell-sized droplet assemblies with user-defined re-writable two-dimensional patterns of functional droplets.