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Molecular π-stacked chromophores are promising photonic materials, but much of our understanding is limited to covalent dimers. Now it has been shown that, in a slip-stacked perylenediimide trimer, coherent vibronic coupling to high-frequency modes facilitates ultrafast state mixing between the Frenkel exciton and charge-transfer states, which then collapses by solvent fluctuations and low-frequency vibronic coupling, resulting in ultrafast symmetry-breaking charge separation.
Soft bioelectronic devices have exciting potential applications in robotics, computing and medicine, but they are typically restricted by the requirement for tethers or stiff electrodes. Now, a synthetic nerve has been developed that is bioinspired, wireless and powered by light. By patterning functionalized lipid membrane compartments, information was directionally conveyed using electrochemical signals.
Flexible metal–organic frameworks (MOFs) in which guest uptake and release occur above certain threshold pressures are attractive adsorbents. Now, the gated sorption behaviour of such a zinc-based mixed-ligand MOF has been tuned to match the narrow temperature and pressure range required for safe, efficient acetylene storage by adjusting the ratio of two different functional groups on its benzenedicarboxylate ligands.
Nickel-rich layered oxides, such as NCM622, are promising cathode materials for lithium batteries, but chemo-mechanical failures hinder their practical application. Now the solid-state synthesis of NCM622 has been studied using multiscale in situ techniques, and kinetic competition between precursor decomposition and lithiation has been observed to lead to spatially heterogeneous intermediates and the formation of defects that are detrimental to cycling.
The planar hexazine dianion ring (N62–), which had previously been predicted to exist, has now been synthesized from potassium azide (KN3) under laser heating in a diamond anvil cell above 45 GPa; it remains metastable down to 20 GPa. By contrast, at 30 GPa an unusual N2-containing compound with the formula K3(N2)4 was produced.
In a similar fashion to its macroscopic counterpart, molecular gearing is a correlated motion of intermeshed molecular fragments against one another. Now it has been shown that photogearing can be used to actively fuel molecular gearing motions with light and concomitantly shift the axis of rotation.
Ion pairing is ubiquitous in low-dielectric-constant solvents, but whether it influences the reactivity of common cationic photoredox catalysts has been unclear. However, it has now been shown that ion pairing is responsible for a 4-fold modulation in reactivity in a prototypical Ir(III) complex and is explained by excited-state ion-pair reorganization.
Most chemical glycosylation methods operate by acid-promoted, ionic activation of donors. Now, by exploiting the formation of a halogen-bond complex, the activation of glycosyl donors was achieved via a visible light-promoted radical cascade process, resulting in a general, simple and mild way to build challenging 1,2-cis-glycosidic bonds.
A reduction reaction is usually equated with an electron transfer reaction. Now, ultrafast time-resolved serial femtosecond X-ray crystallography has enabled the visualization of the stepwise structural changes that occur after electron transfers have been observed in the light-triggered reduction of flavin adenine dinucleotide catalysed by DNA photolyase.
A straightforward method for synthesizing optically active α-amino acids from abundant carboxylic acids has been developed. Based on a nitrene-mediated stereocontrolled 1,3-nitrogen shift, this approach provides access to a large variety of unnatural α-amino acids with aryl, allyl, propargyl and alkyl side chains and enables late-stage amination of carboxylic-acid-containing drugs.
Combinatorial high-throughput methodologies can accelerate screening and discovery in biochemistry and biomedical sciences, but they often rely on large-scale analyses, making them time-consuming and expensive. Now, DNA-mediated fusion of single liposomes has been shown to enable the spatially resolved and parallel cargo delivery of subattolitre volumes in a stochastic order of succession.
White phosphorus (P4) is selectively transformed by oxidative onioation into salts of P1-transfer reagents that feature reactive P–N bonds. These P1 compounds can be used in P–N, P–O and P–C bond-forming reactions to form value-added phosphorus chemicals, representing a viable alternative to the most relevant, yet problematic, P(III) precursor, namely PCl3.
Halogen-bonded co-crystals of a fluorinated azobenzene derivative and a volatile co-former can be cut, carved or engraved with micrometre-scale precision using low-power visible light. The proposed mechanism involves the local evaporation of the volatile component followed by recrystallization of the azobenzene co-former near the edge of the irradiation area.
Influencing the products of a reaction through controlling the state of the reactants is a notable goal for chemists. It has now been shown that the reactivity of a pair of Fermi-coupled vibrational states of CH3D(v1-I and v1-II) with a chlorine atom depends not only on the constituent basis modes, but also on the relative phase of the two modes in their wave-functions.
Although cobalt–carbene radicals have proved to be highly versatile intermediates for homogeneous catalysis, their spectroscopic detection and characterization have been limited. Now, by using hypervalent iodonium ylides, the formation and spectroscopic detection of a biscarbenoid N-enolate–carbene radical—which undergoes a complex catalytic pathway involving reversible N-enolate formation—has been demonstrated.
Molecular energy transfer is thought to follow a simple rule of thumb: high energy transfer requires hard collisions that result in backscattering. However, now it has been observed that an unexpected forward scattering occurs in NO–CO and NO–HD collisions even for high energy transfer. This is attributed to ‘hard-collision glory scattering’, a mechanism that appears to be ubiquitous in molecule–molecule collisions.
Although carbometallation reactions have been thoroughly investigated, understanding the factors responsible for the reverse reaction (β-carbon elimination) is an emerging area of research. Now, a series of substrates has been investigated to study the key factors that promote β-carbon elimination under palladium catalysis.
Information is physical, but the flow between information, energy and mechanics in chemical systems remains largely unexplored. Now, an autonomous molecular motor has been analysed with information thermodynamics, which relates information to other thermodynamic parameters. This treatment provides a general thermodynamic understanding of molecular motors, with practical implications for machine design.
A wide variety of covalent organic cages and two- and three-dimensional covalent organic frameworks have been obtained through dynamic covalent chemistry, yet the synthesis of their one-dimensional counterparts has remained challenging. Porous covalent organic nanotubes have now been prepared through reversible aldehyde–amine condensation and it has been shown that these can further assemble into toroidal architectures.
The s-orbital mixing into the spin-bearing d orbital associated with a molecular Lu(II) complex is shown to both reduce spin–orbit coupling and increase electron–nuclear hyperfine interactions, which substantially improves electron spin coherence. Combined with the potential to tune interactions through coordination chemistry, it makes this system attractive for quantum information applications.
