Luminescent network: Colloidal excimer superstructures with unique optical and electronic properties have recently been described. Ground-state gold cluster cores were held together by the hydrogen-bonding network formed by their capping ligands, which enabled excimer formation.

Split up: Organic conjugated photocatalysts provide an emerging platform for sustainable H₂ production, through water splitting, by artificial photosynthesis. The catalysts have unique properties, including light weight, low cost, accessibility, and fine-tunability of chemical composition, electronic structure, surface properties, and texture.

Nanoreactors in microemulsions are ideal for the synthesis of high-quality inorganic nanoparticles, including bimetals, hollow nanospheres, base metals, peroxides, and metal nitrides. This Review illustrates some options beyond the standard microemulsion synthesis of nanoparticles.

Mission possible: Advanced NMR spectroscopic data support the mechanism proposed for a highly enantioselective acylation reaction. The pocket-like structure of the catalyst is structurally affected upon the addition of the preferentially acetylated diol substrate and key dispersion interactions between catalyst and substrate were uncovered by a newly developed pure shift EASY ROESY experiment.

Yellow phyllobilins shake hands: Natural yellow phyllobilins occur in fall leaves and represent medium-responsive “double-duty” photoswitches. In the presence of light, they undergo E/Z isomerization in polar environments and [2+2] cycloaddition reactions in apolar and membrane-mimetic media. The fascinating chemistry of these phyllobilins suggests yet elusive roles in plants.

Mixed precious metal clusters: The two discrete silver(I)-palladium(II)-oxo nanoclusters, {Ag₄Pd₁₃} and {Ag₅Pd₁₅}, are the first examples of noble metal-capped polyoxo-noble-metalates, featuring an unprecedented host–guest bonding mode comprising hetero- and homometallic Ag–Pd and Ag–Ag bonding interactions. Theoretical calculations suggest that the Ag–Pd metallic bonds originate partially from surface confinement that is induced by strong electrostatic forces.

Pure and simple: Highly pure oxo-functionalized graphene is efficiently synthesized by the use of PTFE equipment. The structural integrity of the underlying carbon framework is confirmed by atomic-resolution transmission electron microscopy and the gently electron-beam induced release of surface functional groups is systematically studied as an alternative approach to chemical reduction.

Acids for base building: A highly diastereoselective and enantioselective Brønsted acid catalyzed reductive condensation of N−H imines was developed. This dimerizing reduction is catalyzed by a chiral disulfonimide (DSI), uses Hantzsch esters as a hydrogen source, and delivers useful C₂-symmetric secondary amines.

Two phosphorescent binuclear C^C* cyclometalated Pt^II complexes bridged by N,N-diphenylformamidinate ligands were synthesized and characterized by 2D NMR experiments, mass spectrometry, DFT calculations, and solid-state structure analysis. The bridging amidinate ligands bring the two platinum centers into close proximity, which leads to extraordinary photophysical properties.

Merger-mania: The title reaction is a rare example of merging N-heterocyclic carbene (NHC) catalysis with single-electron chemistry, a challenging topic with limited previous success. Carbon-centered trihalomethyl radicals have been demonstrated, for the first time, to be compatible with an NHC-bound intermediate, thus leading to efficient and regioselective intermolecular C−C bond formation.

Simple aryl(triethyl)silanes are demonstrated to undergo cross-coupling with iodoarenes to form biaryls and teraryls. The reaction is characterized by a diverse substrate scope, including 4,7-bis(triethylsilyl)-5,6-difluorobenzothiadiazole and thiophene derivatives, and the use of CuBr₂ as a crucial catalyst. The employed aryl(triethyl)silanes are accessible by Ir-catalyzed C−H silylation.

How to Cope with a synthesis problem: Total synthesis of oxygenated, polycyclic terpenes is widely studied, although synthetic strategies that allow for controlled placement of oxygen atoms and other functionality remains a challenge. Here presented is a simple, scalable, and tunable synthetic strategy to assemble terpenoid-like polycycloalkanes from cycloalkanones, malononitrile, and allylic electrophiles.

All the hype: Oxyarylation and aminoarylation were achieved in hypervalent iodine(III)-mediated oxidation of (E)-6-aryl-1-silyloxylhex-3-ene and the corresponding sulfonylamide substrate, respectively. A lactate-based chiral hypervalent iodine(III) reagent was used in the presence of boron trifluoride diethyl etherate, and the products were obtained with good to high enantiomeric excess.

Not satisfied with an observer role, the counteranion determined the outcome of the copper-catalyzed aerobic oxidation of amines to nitriles or imines (see scheme). Selectivity was controlled by ion pairing to the counterion in these reactions, which proceeded at ambient temperature and pressure without expensive ligands or additives.

S-(difluoromethyl)benzene sulfonothioate (PhSO₂SCF₂H) is a powerful reagent for radical difluoromethylthiolation of aryl and alkyl boronic acids, decarboxylative difluoromethylthiolation of aliphatic acids, and a phenylsulfonyl-difluoromethylthio difunctionalization of alkenes under mild reaction conditions.

A new challenger: Aryl amines are synthesized in a metal-free reaction between unsymmetrical aryl(2,4,6-trimethoxyphenyl)iodonium salt electrophiles and alicyclic amine nucleophiles. Yields and scope exceed those of the classical S_NAr approach. The reaction conditions are mild and lead to highly regiospecific substitution of the iodonium moiety in the iodonium reagents.

It's RNAs’ world: Geological strata show that Ca²⁺ does not take phosphate to form prebiotically unreactive apatite if borate, SO₄²⁻, and Mg²⁺ are present. Rather, phosphate is sequestered in the mineral lüneburgite. Upon evaporation, lüneburgite converts ribonucleosides regiospecifically to their phosphates. Thus, borate solves many problems in the synthesis of prebiotic RNA.

Reactive cobalt clusters: The octahedral Co₆–hydride cluster Co₆H₈(PⁱPr₃)₆ and the square-planar Co₄ cluster Co₄{N(SiMe₃)₂}₄ were synthesized from the reactions of a Co^II amide complex with pinacolborane in the presence and absence of PⁱPr₃, respectively. The Co₆–hydride cluster catalyzes the conjugate hydrosilylation of 2-cyclohexen-1-one.

Together forever: High-field ⁶⁷Zn solid-state NMR spectroscopy reveals the synergy between active sites in Zn-modified ZSM-5 zeolites. The internuclear spatial proximity/interaction between Zn²⁺ ions and Brønsted acid sites of the zeolites leads to a synergic effect in the C−H bond activation of methane.

A PANacea: A low-cost, single-step synthesis has been developed to induce the hydrolysis of electrospun polyacrylonitrile (PAN) nanofibers to take advantage of their capability for bringing about in situ N-doping. The resulting N-doped carbon@CoS coaxial nanotubes show excellent lithium and sodium storage.

Why do batteries fail? To study the performance fading of Li–S batteries, the nanoscale processes at a highly oriented pyrolytic graphite (HOPG) cathode/polysulfide-electrolyte interface were directly observed by using in situ AFM and spectroscopic methods. The morphology and growth processes of insoluble products Li₂S₂ and Li₂S were monitored and provided evidence for a mechanism for capacity fading.

Direct formation of a C–C bond: By using a combination of UV/Vis spectroscopy, mass spectrometry, and advanced NMR spectroscopy, evidence was found for the formation of methyl acetate, dimethoxymethane and surface acetate species during the methanol-to-olefin (MTO) reaction over the zeolite catalyst H-SAPO-34. New insights in the formation of the first carbon–carbon bond during the MTO process are provided.

Metal-free CO prodrugs: An intramolecular inverse electron-demand Diels–Alder reaction was employed for developing organic CO prodrugs with tunable release rate and fluorescence formation upon CO release. These prodrugs showed anti-inflammatory effect in Raw 264.7 cells and an induced colitis mouse model.

Looking like a true survivor: The discovery of a robust cyclohexanone monooxygenase (CHMO) that shows great promise as an oxidative biocatalyst is reported. This enzyme (TmCHMO) efficiently converts a variety of aliphatic, aromatic, and cyclic ketones, as well as prochiral sulfides, and was found to be much more thermostable and solvent tolerant than known CHMOs.

Get into the (minor) groove: Enzymatic synthesis of minor-groove-modified DNA was achieved through the polymerase-catalyzed incorporation of 2-substituted 2′-deoxyadenosine nucleotides. Postsynthetic minor-groove labelling was subsequently carried out through thiol–ene or CuAAC reaction of the vinyl-modified or ethynyl-modified DNA, respectively.

Click together: Through the click reaction of tailored dithiols and divinyl ethers, functional polymers containing both main-chain (carbonate, zwitterion) and pendant (diol) functional groups were synthesized. The thioethers in these polymers were quantitatively oxidized to yield either sulfoxides (with aqueous H₂O₂) or sulfones (with m-chloroperoxybenzoic acid), thus further adding to the overall polymer functionality.

A temperature drop: A self-powered temperature and force sensor is based on the reverse electrowetting effect and the thermogalvanic effect of a liquid droplet. The drop is sandwiched between two plates. The degree of force and temperature applied to the top plate can be converted into a response. It has promising applications in a wide range of artificial intelligence systems.

Let's move fast: A universally applicable single-proton relaxation dispersion method was developed to advance the measurement of dynamics in biological molecules. No selective labeling is required and dynamics on timescales down to 20 μs are accessible, thereby enabling the characterization of excited states in RNA, DNA, and proteins by NMR.

A plug-and-play approach to fabricate hybrid π-sheet/helix, π-sheet/coil, and helix/coil architectures by directional self-assembly is reported. On a basic level, these dynamic diblock architectures featuring hybrid topologies of coils, helices, and/or π-stacked sheets mimic protein structural motifs in fully synthetic systems.

Sense and sense ability: The detection of hydrogen sulfide at room temperature using the metal–organic framework (fum-fcu-MOF) as a sensitive layer deposited on capacitive interdigitated electrodes is demonstrated. H₂S concentrations down to 100 ppb were detected with a limit of detection around 5 ppb.

Protein-sized fluorescent nanoparticles were developed, in which PEGylated cyanine bis-azides form a covalently attached corona on micelles of amphiphilic calixarene bearing alkyne groups. The obtained 7-nm nanoparticles are circa twofold brighter than quantum dots 585. FRET studies suggest that they are highly stable in aqueous and organic media as well as in living cells, in which they show excellent imaging contrast.

Catalysis conundrum cracked computationally: The enantioselectivity of asymmetric Lewis acid organocatalysis of the Diels–Alder cycloaddition of cyclopentadiene to cinnamates arises from stacking interactions that favor the addition of the diene to the more hindered face of the dienophile, while electrostatic interactions control the diastereoselectivity by selectively stabilizing the endo transition state.

Magnetic heating: Iron carbide nanoparticles displaying unprecedented heating power were synthesized. Associated to a catalytic metal, these nanoparticles are able to efficiently achieve the magnetically induced hydrogenation of carbon dioxide to methan in a dedicated continuous-flow reactor. Magnetic induction can be successfully applied in heterogeneous catalysis, and in particular to the chemical storage of intermittent energies.

A germane approach to stabilization: A germylene stabilized by homoconjugation is described. The structural parameters and a theoretical analysis of the bonding situation revealed a homoconjugative interaction between the C=C bond and the empty Ge 4p orbital. Reactivity studies confirmed its nucleophilic character, and bimetallic hafnium/iron and hafnium/tungsten complexes were synthesized.

Sparse nitroxide spin-labeling of symmetric, fully deuterated multimeric proteins extends DEER distance measurements up to 170 Å. This is achieved by increasing the length and amplitude of the slow component of phase memory relaxation, thereby permitting DEER data to be collected out to longer evolution times. The approach is demonstrated on the GroEL chaperone comprising 14 identical subunits arranged in two heptameric rings.

Light it up: A dearomative strategy based on the visible-light-promoted para-cycloaddition of arenophile with arenes and in situ diimide reduction was developed that provides access to 1,3-cyclohexadienes or unsaturated 1,4-diamines. These products are complementary to known dearomative processes and are amenable to further diversification.

A supramolecular polymer system based on a cucurbit[8]uril (CB[8]) host and cyanostilbene guest was designed and showed photoluminescence quantum yield of 91% upon complexation in water, without the use of organic solvents or harsh conditions. This robust response opens up new applications in fluorescence bioimaging and sensors.

An assembly-line synthesis involving iterative lithiation-borylations enabled a short, highly enantio- and diastereoselective synthesis of tatanan A, and its C3 epimer. High substrate-controlled diastereoselectivity with a lithiated primary benzyl benzoate furnished the C3 epimer. A complete switch in selectivity was achieved using a novel substrate-controlled diastereoselective Matteson homologation to provide access to the natural product in only eight steps.

Gels and batteries: The “double-helix” structure in carrageenan–metal hydrogel was used as a new precursor for making the multiple metal sulfides/carbon aerogels with ultra-small nanoparticles and hierarchical porous structure. These aerogels exhibit high reversible capacity, excellent rate ability, and cycling stability for sodium-ion batteries.