Recent advances in photochemical C−H functionalization reactions using a single metal catalyst to enable sustainable strategies for the functionalization of C−H bonds under ambient conditions without an external photosensitizer are highlighted in this Minireview. Reaction mechanisms and the role of visible light are described, and future perspectives and challenges to stimulate future research directions in the field of light-mediated C−H functionalization are discussed.

Oxidative fluorination of various Group 15, 16, and 17 heteroatoms in organic scaffolds was made significantly more accessible in recent years using potassium fluoride and trichloroisocyanuric acid (TCICA)—a common swimming pool disinfectant. Behind-the-scenes insight and discussion on discoveries, applications, and opportunities associated with this “TCICA/KF approach” are chronicled herein.

Red-shifted photoswitches are in high demand and have sparked great research interest in the past decade. In this Review, we highlight recent progress towards the development of visible- and NIR-activated photoswitches characterized by distinct photochromic reaction mechanisms. We evaluate the pros and cons of each type based on their photochromic properties and conclude with a perspective on how the field may develop in the future.

Photodegradable, recyclable, and renewable crosslinked polymers from bioresources show promise towards developing a sustainable strategy to address the issue of plastic degradability and recyclability.

A 14-step approach to (+)-cochlearol B is reported. The strategy involves an organocatalytic Kabbe condensation, Catellani reaction, and visible-light-mediated [2+2] cycloaddition to rapidly access the core of this natural product. Careful design and tuning of the Catellani and photocycloaddition reactions proved crucial in overcoming undesired reactivity, including cyclopropanation reactions, and [4+2] cycloadditions.

The integral membrane protein assembly Aquaporin-0 was analysed by native ambient mass spectrometry of eye lens tissue. Membrane protein assemblies were solubilised by detergent micelles. Spatially-resolved analysis for mapping protein assembly distributions, accurate intact mass determination, and the identification of assemblies approx. 100 kDa in molecular weight are demonstrated.

A novel Ag^I-DNA rod comprising a one-dimensional array of 11 silver ions within a double-helical structure was obtained by mixing an oligonucleotide and silver ions in appropriate solutions. Furthermore, formations of the rod structure in solutions were determined by UV/Vis, CD, NMR, and mass spectrometry.

Simple building blocks were used for the total synthesis of miharamycin B and its biosynthetic precursor. The key step in the strategy was the de novo construction of the pyranose moiety through Achmatowicz rearrangement. The purine ring was introduced by palladium-catalyzed N-glycosylation.

A practical method for the catalytic asymmetric synthesis of silicon-stereogenic silanols has been developed. This direct catalytic asymmetric hydrolytic oxidation of dihydrosilanes gives access to a variety of functionalized silicon-stereogenic silanols, including bis-silanols, in high yields with excellent chemo- and stereoselectivity under ambient conditions.

Simple and readily available alkyl sulfoxides are shown to be suitable precursors to radicals. Alkyl sulfoxides, N-methoxy pyridinium salts and fluoride anions form electron donor–acceptor (EDA) complexes, which, upon visible-light irradiation, undergo a radical chain process to give various pyridine derivatives.

A modular and step-economical approach based on a three-component Catellani reaction and a gold(I)-catalyzed cyclization/reduction cascade has been established for the diversity-oriented synthesis of 1,3-trans-disubstituted tetrahydroisoquinolines. This synthetic strategy enabled concise syntheses of an analogue of the new drug mevidalen as well as four naphthylisoquinoline alkaloids.

By engineering a bacterial sirtuin deacetylase with thiol-bearing noncanonical amino acids, a selective and robust covalent binder for lysine crotonylation on proteins was developed, and features a unique NAD⁺ dependency.

Metallogels based on the co-assembly of L-glutamic acid lipids with cobalt ions can be used as catalysts for photocatalytic CO₂ reduction presenting high efficiency and good product selectivity. Mimicking the natural lipid bilayer not only provides these soft matter catalysts with a hydrophobic microenvironment and binuclear synergistic effect but also renders them environmentally friendly with recycling and degradable properties.

The first N-heterocyclic boryl-stabilized disilyne has been prepared and structurally characterized. The disilyne compound enabled the activation of dihydrogen and the benzylic C−H bond from toluene without the need for a catalyst, highlighting the unique electronic effects of the boryl group on the properties of low-valent silicon species.

A monomeric Al^I compound is used as a stoichiometric reducing agent towards a series of Al^III dihydrides. This leads to the formation of new low oxidation state species including symmetric and asymmetric dihydrodialanes, and a masked dialumene. The transient formation of new, previously inaccessible Al^I species is demonstrated through reactivity studies and theory.

The metallic compositions of nanoclusters can dictate whether their photoluminescence is fluorescence or phosphorescence. This effect is demonstrated with Au₅Ag₁₁ and Pt₁Ag₁₆ nanoclusters that have comparable structures but different compositions.

A complex combining an ambiphilic carbene/xanthylium ligand and a gold trichloride supports the efficient green-light-induced extrusion of chlorine radicals en route to the corresponding gold(I) complex. The photolability of this gold(III) complex originates from excitation of a carbene/xanthylium donor/acceptor dyad, the excited state of which challenges the inherent stability of the gold(III) moiety.

Formal β-C−H (hetero)arylation of aldehydes and ketones via their readily prepared silyl enol ethers has been achieved by dual nickel and photoredox catalysis. This reaction features broad scope and excellent functional group tolerance.

The enantioselective hydrocarbamoylation of alkenes enabled by copper hydride and palladium cooperative catalysis was developed. Utilizing readily available carbamoyl chlorides, this method can be applied to various types of olefins, including alkenyl arenes, terminal alkenes, and 1,1-disubstituted alkenes, providing α- and β-chiral amides in good yields with excellent levels of enantioselectivity.

A chiral perylene bisimide (PBI) hetero-cyclophane comprising a chiral binaphthol bisimide (BBI) dye and a dynamically racemic PBI dye shows quantitative energy and solvent-dependent chirality transfer among its components, thereby leading to an amplified bright red circularly polarized luminescence from PBI.

At the intersection of molecular recognition and materials science, a multi-functional two-dimensional covalent organic framework (COF) is prepared and applied as a broad-spectrum adsorbent for the high-efficiency removal of per- and polyfluoroalkyl pollutants.

The exceptionally rapid degradation of microplastics (MPs) in frozen solution was discovered. The activity is ascribed to selective generation of singlet oxygen in the narrow space of the liquid layer between ice crystals. The findings offer a highly efficient degradation pathway for MPs and shed light on mechanisms of disposal of MPs in nature.

A novel amino acid synthon in the form of boronoalanine (Ala^B) suitable for umpolung peptide/protein functionalization is described. It is demonstrated that Ala^B can be incorporated into peptides and proteins, and remains stable under solid-phase synthesis, native chemical ligation, and radical desulfurization. Furthermore, Ala^B is a competent partner in inter(intra)molecular C(sp³)−C(sp²) cross-couplings.

Reductive carbon–carbon coupling was used to block H₂ evolution in CO₂ photoreduction in water. Furfural, one of the biomass platform molecules, adsorbs on Zn-sites consuming electrons and protons originally used for H₂ production, but the CO formation pathway at surface anion vacancies remains. Therefore, CO was evolved with a CO/H₂ ratio of 265 : 1 in the gas phase and furfural was upgraded to value-added hydrofuroin.

The discovery of a new [1,5] sigmatropic rearrangement is described. With the aid of a borane-based Lewis acid, the transiently generated C3 ammonium enolates undergo a sigmatropic [1,5] shift of benzylic, allylic and propargylic groups to provide access to trans-configured tetrahydroquinoline-4-ones with diastereoselectivity of >99 : 1. The reaction is investigated in kinetic, mechanistic and computational experiments.

Stable compounds with a genuine B=P double bond are rare and have limited applications given their protecting groups′ bulky nature. The preparation of a Lewis base-stabilized phosphaborene with a B=P double bond and a trimethylsilyl (TMS) functionality at the P-terminal is reported, which exhibits an unprecedented ability for B=P-unit transfer reactions, allowing the isolation of B=P-containing compounds.

Polyfunctional dicarbamoylzincs of type (R¹R²NCO)₂Zn were prepared in THF by treating a mixture of formamides and ZnCl₂ with LiTMP (THF, 15 °C, 15 min) or by reacting formamides with TMP₂Zn (THF, 25 °C, 16 h). These zinc reagents reacted with allylic, benzylic, aryl and alkenyl bromides, acid chlorides, aldehydes or enones providing various amides in 47–97 % yields. ¹³C NMR data showed a characteristic carbonyl signal at 219.4 ppm for (Bu₂NCO)₂Zn.

Although doubted in the past, two π-electrons are just enough to stabilize five-membered aromatic compounds that are even stable at room-temperature, as shown by the facile synthesis of a dipotassium cyclopentagallene. This compound is a unique example of a five-membered aromatic ring stabilized by only two π-electrons. Single-crystal X-ray diffraction revealed a planar Ga₅ ring with almost equal gallium–gallium bond lengths.

Cryo-cooled water molecules block protein motions that impact protein–ligand interactions. Paired cryo and room-temperature comparisons of ligand-bound Hsp90α structures show that water networks and protein conformations are more mobile at room temperature. Revealing such alternate conformational states that are masked by cryo-cooling provides new insights towards drug discovery.

A novel ternary alloy PtWMn nanoplatform is developed as a Mn reservoir that exhibits efficient storage, specific delivery and accurate release of Mn ions for high-specificity ferroptosis-based cancer therapy. Such a smart nanoplatform can exert a responsive imaging signal in dual-mode (T₁- or T₂-weighted) high-field MRI, which enables the real-time monitoring of Mn release within the tumor microenvironment and of ferroptosis initiation.

Catalyst engineering enables the single-pot integration of solid nanoparticulate and molecular cobalt catalysts in a slurry-phase tandem Fischer–Tropsch synthesis/olefin reductive hydroformylation process for a direct and highly selective conversion of syngas (H₂/CO) to higher alcohols. The new tandem process contributes to bridging the traditionally dissevered disciplines of heterogeneous and homogeneous catalysis.

A new catalyst platform for C(sp³)−H bond functionalization has been discovered. “Sandwich” diimine-copper(I) complexes catalyze reactions of alkane, ether, and amine C−H bonds with a large panel of diazo compounds. Additionally, the first metal-catalyzed C(sp³)−H methylation by CH₂N₂ is disclosed. The electrophilicity and extreme steric bulk of these catalysts are likely reasons for their efficiency.

Aptamer sgc8c equipped with an ATP-responsive protection module, termed ARP-sgc8c, was designed. ARP-sgc8c could be selectively protected from nuclease degradation in the tumor microenvironment through specific incorporation along with high-concentration ATP, while its rapid degradation was maintained in healthy tissues.

A highly efficient meta-selective C−H arylation of aryl ethers has been realized by a new catalytic system based on palladium/norbornene (Pd/NBE) and an S,O-ligand. The reaction proceeds with a broad range of aryl ethers. For the first time, unsymmetrical meta-diarylation of aryl ethers was accomplished using a novel norbornene. The isolation of palladium intermediates provides insight to the mechanism.

Four ketoreductases (KREDs) were identified for the enantioselective synthesis of β-hydroxysulfides. KRED311 and KRED349 catalyse the synthesis of β-hydroxysulfides bearing a stereocentre at the C−O bond with opposite absolute configurations via chemoenzymatic cascades from thiophenols/thiols and α-haloketones/alcohols. KRED253 and KRED384 catalyse the synthesis of β-hydroxysulfides bearing a stereocentre at the C−S bond with opposite enantioselectivities by dynamic kinetic resolution (DKR) of racemic α-thioaldehydes.

Sustainable organic afterglow room-temperature phosphorescence (RTP) with long lifetime is a particularly attractive phenomenon but remains difficult to achieve. Here, we prepared sustainable afterglow RTP materials (GA@SA) with a lifetime up to 934.7 ms by embedding gallic acid (GA) within a Ca²⁺-crosslinked sodium alginate (SA) matrix.

Various aromatic sulfonic acids and amines were self-assembled by charge-assisted hydrogen bonding to form porous organic salts. This study demonstrates the advantages of diverse porous organic salts, such as all-organic, extremely facile preparation methods, diverse void structures and environments, and excellent CO₂ adsorption properties.

A Büchner–Curtius–Schlotterbeck-type reaction enabled the total synthesis of tunicamycin V (TN-V), a nonselective phosphotransferase inhibitor, in just 15 steps from D-galactal in 21 % overall yield. The short and high-yielding synthetic route was also adapted for the synthesis of analogues, thus leading to the discovery of a novel cytostatic tunicamycin analogue, TN-TMPA, with high DPAGT1 selectivity.

A combination strategy for synergistic chemo-sensitization and conversion of tumor cells into vaccines triggers an intense immune response through copper chaperone inhibition with multifunctional nanoparticles loaded with cisplatin prodrugs and DC_AC50 conjugated to reactive oxygen species (ROS)-responsive polymers.

During polarized light illumination, a floating azo-film experiences a wealth of ultrafast wrinkling evolution coupled with unprecedented sequential wrinkling orientation conversion (from polarization-parallel to polarization-perpendicular). The different polarization-dependent sequential photo-orientation for azo side chains and azo-grafted main chains of azopolymers that are involved is revealed experimentally for the first time.

The highly reversible electrochemical conversion of commercial bulk copper metal to form basic copper carbonate, Cu₂CO₃(OH)₂, from a saturated aqueous electrolyte comprising 4.5 m K₂CO₃ and 9 m KOH, demonstrating high capacity, fast rate capability, and relatively stable cycle life is reported. The salt electrode consisting of Cu, K₂CO₃, and KOH renders this anion-hosting electrode a cathode for rocking-chair batteries.

An electrochemical neutralization chemistry strategy that couples acidic hydrogen evolution and alkaline hydrazine oxidation with ionic exchange enables utilization of the chemical energy and low-grade heat from the surroundings for hydrogen production with electricity output.

An innovative reaction strategy for the transformation of methane into acetic acid via CH₃Cl carbonylation over H-zeolites is reported. A 99.3 % acetic acid (AA) and methyl acetate (MA) selectivity was obtained over pyridine-pretreated MOR at 523 K and 2.0 MPa. This strategy enables efficient conversion of methane into oxygenates under mild conditions.

We have demonstrated the first fast-scanning potential-gated organic electrochemical transistor (FSP-OECT) for in vivo dopamine (DA) sensing, featuring high sensitivity, selectivity, reproducibility, and stability. It was successfully applied for in vivo DA sensing at low basal levels as well as the electrically stimulated release of DA.

A rapid, simple, and reagent-less dual-electrode electrochemical chip (DEE-Chip) was developed using a barcode-releasing electroactive aptamer for on-farm detection of porcine epidemic diarrhea viruses (PEDv). This biosensor demonstrated a diagnostic sensitivity of 83 % and specificity of 100 % using 12 porcine saliva samples with a concordance value of 92 % at an analysis time of one hour.

Different from the previously known hydroborative cyclizations that add hydrogen and boron to opposite sides of an enyne, the proper choice of a ruthenium catalyst alters this propensity to a new addition mode, geminal hydroborative cyclopropanation. Two possible mechanisms are operative, which are substrate-dependent based on DFT studies.

The use of a dimeric silver trifluoroacetate template, has facilitated a “rim-differentiated” pillar[6]arene to be isolated successfully from a mixture containing eight constitutional isomers. This macrocycle exhibits interesting conformational adaptation toward guest molecules in the solid state.

An efficient method to manipulate electron spin orientation in single molecule devices by electrical gating is reported. The realization of such a function is based on a special class of molecules, named bipolar magnetic molecules (BMMs), which are characterized by their unique energy level arrangement, i.e. HOMO and LUMO come from two different spin channels.

A new Li−N interaction induced 1,2-dimethylimidazole (DMIm)-based deep eutectic gel polymer electrolyte is reported. The electron-donating DMIm dissociates LiTFSI well to form a deep eutectic electrolyte (DEE). The incorporation of polyvinylidene difluoride (PVDF) further changes the coordination environment of the Li⁺ ions. This kind of gel polymer electrolyte exhibits high ionic conductivity and electrochemical stability and enables the excellent long-term cycling performance for Li/LFP cells.

The atroposelective electrophilic amination of indoles catalyzed by a chiral phosphoric acid (CPA) is reported. The reaction proceeds by asymmetric 1,6-addition to p-quinone diimines to deliver atropochiral N-sulfonyl-3-arylaminoindoles in good yields and with excellent ee values.

A DNA-based strategy is developed for spatially-selective amplification of acidic signals in the extracellular milieu of tumors. Amplified imaging of the tumor microenvironment with improved sensitivity was achieved by acidity-responsive engineering of the cell surface with DNA receptors for controlled recruitment of fluorescent amplifiers.

Competitive CO₂ capture in a porous organic cage membrane can be assisted by ionic liquid molecules (e.g., BMIMBF₄). Ionic liquid molecules electrostatically induce the crystal-rearrangement of cage molecules to construct regular nanochannels as well as aiding in situ nanochannel regulation.

A nickel-catalyzed switchable site-selective alkene hydroalkylation was developed. The selection of reaction temperatures led to protocols that provide regiodivergent hydroalkylated products starting from a single alkene substrate.

A simple synthesis of P-heterocycles featuring an internal ylidic bond is reported. The stability of the compounds tolerates post-functionalization (direct arylation) and the strategy is also compatible with the preparation of polyaromatic scaffolds (acenes, helicenes). Molecular engineering allows tuning the optical and redox properties, making them valuable dyes for a large panel of photonic or opto-electronic applications.

The unique synthesis of a boryl-substituted borole system by means of a 1,1-hydroboration/1,1-alkenylboration sequence provided access to the unprecedented 1-bora-3-boratabenzene class of compounds.

A selenium-doped polycyclic organoboron emitter exhibits ultrafast triplet–singlet exciton interconversion ability in addition to strong narrowband blue emission. Its spin-flip reverse intersystem crossing (RISC) rate exceeds 10⁸ s⁻¹ (100 million times spin inversion per second), enabling superimposed fluorescence with full exciton utilization. This breakthrough shatters the stereotypical physicochemical views of conventional thermally activated delayed fluorescence limited by slow RISC.

Donor–acceptor alternating conjugated polymers with various electronic characteristics, including strong donor–strong acceptor, are synthesized via living Suzuki–Miyaura catalyst-transfer polymerization in a controlled manner. The polymerization also works with a complex quateraryl monomer and allows for one-pot di(tri)block copolymer synthesis. The resulting polymers have tunable optical and electrochemical properties based on the combination of building units.

Strong electronic interactions between hexagonal boron nitride (h-BN) and Cu₂O protect the Cu−O bonds against electron attack through the transfer of accumulated electrons from Cu₂O to h-BN. This effect stabilizes the active Cu⁺ species during CO₂ electroreduction.

A nanostructured Li₂S−Cu composite is fabricated and it is demonstrated that Cu progressively participates in the redox processes and fundamentally alters the redox couple from anion-type Li₂S/S to cation-type Cu/Cu₂S, which leads to a drastically reduced activation potential (2.35 V vs. Li⁺/Li), superior rate capability, and stable long-term cycling performance.

Beginning with cation-vacancy controllable LiNiO₂, the origin of the high performance and the structure–activity correlations was studied. The results indicate that lattice oxygen activated by cation vacancies triggered charge disproportionation to form high-activity Ni⁴⁺, resulting in facilitating deprotonation in a lattice oxygen involved catalytic process.

A method for late-stage peptide ligation and macrocyclization through rhodium-catalyzed C7-selective alkylation of tryptophan residues has been developed. This method is compatible with internal olefins and represents the first example of site-selective peptide C−H alkylation through deconjugative isomerization.

Bioinspired metalation of the MOF MIL-125-NH₂ was accomplished by incorporating the electron-transfer unit of a Rh complex for facilitated photocatalytic NADH regeneration. By immobilizing formate dehydrogenase onto the hydrophobic layer of the membrane, a gas-liquid-solid three-phase interface around the enzyme site could be formed for sustained and enhanced formic acid production coupled with in situ generated NADH.

An efficient method for the atroposelective construction of nine-membered carbonate-bridged biaryls was achieved through a ring-expansion process via vinylidene ortho-quinone methide (VQM) intermediates. This strategy allows the convenient construction of bridged biaryls with broad functional group tolerance under mild conditions. In bioassay studies, several agents showed considerable antiproliferative activity via the mitochondrial-related apoptosis mechanism.

A brand new eutectic electrolyte consisting of ethylene glycol (EG) and ZnCl₂ has a unique solvation structure and could enable the formation of a Cl-rich organic–inorganic hybrid solid electrolyte interphase film on a Zn anode, realizing highly reversible Zn plating/stripping.

An unusual C_5h-symmetric silver nanocluster (Ag155) with the highest reported nuclearity was prepared by exploiting the protection of the macrocyclic ligand p-tert-butylthiacalix[4]arene (H₄TC4A) and cyclohexanethiol (CySH). This silver nanocluster exhibits excellent stability in solution and photothermal conversion efficiency.

The galactose-modified zirconium metal–organic framework ZTIG, which has high order multi-photon excited fluorescence properties, can realize NIR-II excited fluorescent imaging and photodynamic therapy.

Mechanistic insight into the isomerization synthesis of sila-adamantane enables the regioselective functionalization of sila-adamantane at its 1-, 2-, 3-, 5-, and 7-positions. Substitution at the 1-position of the cluster core significantly impacts optical absorbance relative to exocyclic or 2-substitution.

A promising approach towards optically active biohybrid systems that selectively bind receptors of the sialic acid-binding immunoglobulin-like lectins (siglecs) family is described. To this end, siglec-modified supported lipid bilayers act as cell membrane mimics that interact in a multivalent fashion with photosensitizer-loaded vesicles, showing a potential for targeting siglec-expressing cells with photosensitizing nanocarriers.

Phase-pure, colloidally stable Cu₃N and Cu₃PdN were obtained. The precursor conversion mechanism is elucidated; oleylamine is oxidized to a primary aldimine and the latter reacts further with oleylamine to a secondary aldimine, eliminating ammonia. Ammonia reacts with Cu^I to form Cu₃N.

A two-dimensional polyimide-linked covalent organic framework (COF) with high loading density of redox-active centers and a mesoporous channel for facile Li⁺-ion diffusion has been designed and fabricated, exhibiting one of the best performances among the thus far reported COF-based cathodes for Li-ion batteries.

Pt₁Au₃₇(SCH₂Ph^tBu)₂₄ and Pt₂Au₃₆(SCH₂Ph^tBu)₂₄ nanoclusters are prepared by doping one and two Pt atoms into the kernels of Au₃₈(SCH₂Ph^tBu)₂₄.This study provides an opportunity for systematically investigating the electron configuration change of the nanoclusters in the consecutive doping process and shows the order of electrocatalytic activity: Pt₁Au₃₇ > Au₃₈ > Pt₂Au₃₆.

A special class of helicene-type additives, which are straightforward to synthesize in large amounts, induce strong chirality in polyfluorene copolymer thin films. Advanced chirality-sensitive microscopy techniques and ultrafast time-resolved spectroscopic methods based on transient circular dichroism and transient circularly polarized luminescence reveal the supramolecular origin of the chiroptical properties.

The applicability of a deep eutectic solvent thermomorphic multiphasic system (DES-TMS) within biocatalysis was successfully demonstrated. Horse liver alcohol dehydrogenase was simply recycled using the DES-TMS. At increased temperatures, the system splits into an aqueous-enriched and a DES-enriched phase. In this way, the product and the catalyst were separated in a single unit operation step.