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Model thiophene-decorated nickel porphyrins are synthesized to examine how sulfur promotes CO2-to-CO conversion and tandem CO2-to-C2 product conversion in electrocatalytic CO2 reduction. Combined theoretical and experimental analyses show that thiophene substituents generate a ligand hole character that modulates the nickel-centred electronic structure, enhancing overall catalytic performance.
Charge-selective contacts have a key role in increasing the efficiency of perovskite solar cells (PSCs). A hole-transport material (HTM) is designed based on a symmetric aromatic molecule that facilitates long-range ordered π–π stacking on substrates. This HTM shows enhanced charge-transport properties, and when incorporated into PSCs, helps to deliver good efficiency and stability.
Molecular engineering has increased the power conversion efficiency of inverted perovskite solar cells (PSCs), surpassing that of regular PSCs. Here, the symmetric molecule (2-(pyren-2-yl)ethyl)phosphonic acid (pPy) enables long-range-ordered π–π stacking, enhancing charge transport. pPy films show face-on orientation and uniform distribution, yielding PSCs with power conversion efficiencies of 26.6%.
Photo-electrocatalysis under alternating polarity allows enantioselective redox-neutral cross-coupling through β-scission of alcohols to afford optically pure chiral α-arylated amines.
An alternating current paired photo-electrocatalysis approach, integrating electrochemistry, ligand-to-metal charge transfer photocatalysis and asymmetric nickel catalysis, enables enantioselective C(sp3)–C(sp2) cross-coupling of alcohols. This approach has high catalytic efficiency and stability, achieving up to 99% enantiomeric excess with broad substrate compatibility, and is suitable for late-stage functionalization of complex molecules.
Thianthrene, long used in materials science, has recently emerged as a powerful reagent in organic synthesis. Its unique electronic structure enables access to diverse aryl, alkenyl and alkyl thianthrenium salts, which exhibit reactivity beyond conventional (pseudo)halides. This Review highlights the fundamental properties, distinctive reactivity and synthetic applications of these thianthrenium salts.
A covalent organic framework-based type-II heterojunction (TpPa/TpDz) enables efficient photocatalytic H2O2 production in pure water. The highest and lowest occupied molecular orbitals are spatially separated, driving directional photogenerated carrier transport and minimizing recombination, therefore enhancing photocatalytic activity.
A microinterfacial solvothermal polymerization strategy is developed for irreversible coupling reactions to form porous crystalline sp-carbon-conjugated covalent organic frameworks with diverse topologies. These two-dimensional frameworks exhibit enhanced conductivity and tunable magnetic properties.
A N-heterocyclic carbene–nickel-catalysed dynamic kinetic asymmetric aldehyde–alkyne reductive coupling reaction is reported, achieving control over chemo-, regio-, E/Z-, diastereo-, and enantioselectivity. This approach offers a streamlined route to construct multifunctional allylic alcohols with adjacent stereocentres from readily accessible substrates.
Helicity-overriding behaviour in supramolecular copolymers is reported by manipulating the energy landscape of chiral co-monomers, where one chiral monomer can override the intrinsic helical preference of another, even when present in the minority. This finding offers insights into asymmetry amplification in multicomponent supramolecular systems.
Selective functionalization of methylene C−H bonds at distal positions remains a challenge. Now, through ligand design, the Pd-catalysed activation of distal methylene C(sp3)–H groups in free carboxylic acids for the assembly of γ,δ-benzocyclobutene (BCB) acids is demonstrated. This approach enables the preparation of diverse BCBs from simple starting materials.
The electrosynthesis of amino acids is hindered by inefficient oxime intermediate conversion. Here, a relayed electron transfer mechanism is proposed using an ionic-liquid@Bi catalyst. Electrons are accepted by the ionic liquid to generate related radicals, which then transfer electrons to oxime, enabling efficient amino acid production.
A cooperative electrolytic strategy is designed, enabling dual C–H functionalization of deconstructed polyolefin oligomers, converting carbon fibre-reinforced polymer waste into adaptive materials. This approach forms covalently adaptable networks and establishes electrochemical backbone editing as a versatile platform for advanced polymer design and functionalization.
The synthesis of benzocyclobutenes is reported through Pd(II)-catalysed γ,δ-methylene C(sp3)–H bond activation and [2 + 2] annulation between aliphatic carboxylic acids and dihaloarenes, using bidentate carboxyl-pyridone ligands. Regiocontrol is achieved in benzocyclobutene formation through the differentiation of reactivity between the aryl iodide and bromide sites.
A sustainable two-step strategy for oxime synthesis in a neutral KHCO3 medium is reported. Free-state NH2OH is initially synthesized via nitrite electroreduction over a Ketjen-black-supported iron phthalocyanine catalyst, followed by a chemical aldehyde or ketone oximation using the electrochemically synthesized NH2OH.
Multiple bonds involving heavier elements were considered impossible but have recently been shown to be stable and offer divergent reactivity. Here the isolation of an alumene (a compound containing an Al=C bond) via direct CO reduction is described. Analysis of the alumene and its ability to homologate CO is reported.
