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From atoms and molecules, to supramolecular and nanoscale assemblies; from the gas phase to liquids and crystals, and matter under extreme conditions: this page highlights some of the most exciting works in physical chemistry and inorganic chemistry, aiming to explain the fundamental properties of matter, its response to non-equilibrium conditions, the dynamics of chemical reactivity and bonding behavior.
Tracking single molecule movements is a challenging task, but highly desired for applications and fundamental studies. Here the authors reconstruct the sub-angstrom relative movements of a molecule interacting with a metal adatom, by measuring its vibrational spectrum in a self-assembled monolayer, continuously modified by the adatom in a nanoparticle-on-mirror construct.
Ion storage rings allow reactions to be studied over orders of magnitude in time, bridging the gap between typical experimental and astronomical timescales. Here the authors observe that polycyclic aromatic hydrocarbon fragments produced upon collision with He atoms at velocities typical of stellar winds and supernova shockwaves remain intact up to second timescales, thus may play an important role in interstellar chemistry.
Dynamic nuclear polarization (DNP) greatly improves the NMR sensitivity, but its implementation in aqueous solutions is challenging. Here the authors demonstrate carbon polarization enhancement via in situ Overhauser DNP in small biomolecules in water at room temperature and high magnetic field.
The preparation of nanocages with unprecedented architectures may lead to new functions. Here the authors report the self-assembly of organic cages featuring twin cavities; the geometry and pocket size determine the molecular packing and the proton conductivity performance.
The most common oxidation state for lanthanides is +3. Here the authors use photoelectron spectroscopy and theoretical calculations to study half-sandwich complexes where a lanthanide center in the oxidation state +1 is bound to an aromatic wheel-like B82- ligand.
The stereoselective analysis of mixtures of chiral compounds typically requires time-consuming chromatography. Here, the authors combine reaction based chiroptical sensing and chemometric tools to directly determine the absolute configuration, enantiomeric composition and concentration of convoluted samples without physical separation.
Understanding the source of vibrationally excited molecular hydrogen is an essential prerequisite for understanding the chemical evolution in the universe. Here the authors report a photodissociation pathway to produce vibrationally excited H2 via the water photochemistry.
Polycyclic aromatic hydrocarbons play an important role in interstellar chemistry, where interaction with high energy photons can induce ionization and fragmentation reactions. Here the authors, with XUV-IR pump-probe experiments, investigate the ultrafast photoinduced dynamics of fluorene, phenanthrene and pyrene, providing insight into their preferred reaction channels.
Core-shell designs enhance the luminescence of lanthanide-doped upconversion nanoparticles (UCNPs), but the effect of shell coverage was insufficiently characterized. Here the authors demonstrate, on a series of core-shell UCNPs with various shell coverage ratios, an on-off effect by which luminescence is enhanced only when a full coverage is achieved.
Identifying a concerted or stepwise mechanism in Diels–Alder reactions is experimentally challenging. Here the authors demonstrate the coexistence of both mechanisms in the reaction of 2,3-dibromobuta-1,3-diene with propene ions, using a conformationally controlled molecular beam reacting with trapped ions and ab initio computations
Colloidal self-assembly enables bottom-up manufacture of materials with designed hierarchies and functions. Here the authors develop a facile method to construct multidimensional colloidal architectures via the association of soft block copolymer micelles with simple unvarnished hard nanoparticles.
Controlled breaking of a chemical bond by mechanical forces can provide key insight into reaction mechanisms. Here the authors, using atomic force microscopy and computations, measure the forces involved in breaking a single dative bond between a CO molecule and a ferrous phthalocyanine complex.
The roaming reaction is a common process in the gas phase and in solution, but observation of the involved atomic movements has been challenging. The authors, using femtosecond time-resolved X-ray liquidography, resolve the detailed structural dynamics at the onset of a roaming reaction in the photoinduced isomerization of BiI3 in solution.
Asymmetrically substituted phosphine ligands play a decisive role in catalysis, but their synthesis is rather challenging and often involves hazardous chemicals such as PCl3 or PH3. Here, the authors report the one-pot preparation of asymmetric phosphines from white phosphorus via a pentaphosphaferrocene based modular system, in which the transition metal complex can be reused.
Aqueous solutions under nanoscale confinement exhibit interesting physicochemical properties. This work reports evidence on the spontaneous formation of two-dimensional alkali chloride crystalline/non-crystalline nanostructures in dilute aqueous solution under nanoscale confinement by computer simulations.
In comparison to their neutral or anionic counterparts, examples of cationic boron clusters remain scarce. Here, the authors prepare a variety of cationic polyhedral boranes by reacting closo-10-vertex carboranes with N-heterocyclic carbenes; the resulting open-cage cationic nido- arachno- or closo- derivatives are water soluble, which may enable unprecedented applications.
Determining the covalency of actinide chemical bonding is a fundamentally important challenge. Here, the authors report a 15N nuclear magnetic resonance spectroscopy study of a terminal uranium-nitride, revealing exceptional NMR properties and covalency that redefine 15N NMR parameter space and actinide chemical bonding.
Mechanical motions in hybrid sp2/sp3 -hybrid nanocarbon peapods might lead to promising materials applications, but have been insufficiently explored. Here the authors demonstrate that a diamondoid molecule trapped inside a carbonaceous cylinder undergoes solid-state rotations at terahertz frequencies.
Shock-wave driven reactions of organic molecules may have played a key role in prebiotic chemistry, but their mechanisms are difficult to investigate. The authors, using time-resolved x-ray diffraction and small-angle x-ray scattering experiments, observe the transformation of liquid benzene during a shock, identifying carbon and hydrocarbon solid products.
Tetrel bonds are noncovalent interactions between electron donors and group 14 elements; in these situations, C(sp3) atoms can act as Lewis acids, accepting electron density. Here, the authors show that methyl groups, when bound to atoms less electronegative than carbon, can participate in noncovalent interactions as electron density donors.
The photodissociation dynamics of small molecules in the vacuum ultraviolet range can have key implications for astrochemical modelling, but revealing such dynamical details is a challenging task. Here the authors, combining high resolution experimental techniques, provide a detailed description of the fragmentation dynamics of selected rotational levels of a predissociated Rydberg state of H2S.
Reactions at the interface between mineral surfaces and flowing liquids are ubiquitous in nature. Here the authors explore, using surface-specific sum frequency generation spectroscopy and numeric calculations, how the liquid flow affects the charging and dissolution rates leading to flow-dependent charge gradients along the surface.
Accurate computational prediction of atomistic structure with traditional methods is challenging. The authors report a kernel-based machine learning model capable of reconstructing 3D atomic coordinates from predicted interatomic distances across a variety of system classes.
The preparation of artificial host–guest systems that display dynamic adaptation during guest binding is challenging. Here the authors report a chiral self-assembled tetrahedral cage featuring curved walls that reconfigures stereochemically to fit fullerene guests, regulates corannulene inversion, and enables the determination of co-guest enantiomeric excess by NMR spectroscopy.
Although N-heterocyclic carbenes (NHCs) are a promising class of ligands for forming robust self-assembled monolayers on metals, many questions remain about their behavior on surfaces. Here, the authors address these fundamental questions—such as the factors controlling NHC orientation, mobility, and ability to self-assemble—through an in-depth examination of NHC overlayers on Au(111).
The H3+ ion plays a key role in interstellar chemistry and can be formed from organic compounds upon interaction with charged particles or radiation. Here the authors demonstrate that H3+ can also be formed from water adsorbed on silica nanoparticles exposed to intense laser pulses, conditions that mimic the impact of charged particles on dust in astrophysical settings.
Photon upconversion in lanthanide-doped nanoparticles enables important technological developments. Here the authors demonstrate a mechanism leading to enhanced upconversion emission in core-shell nanoparticles, and long-distance energy transfer between nanoparticles, through triplet state population of an organic surface ligand.
Water ice exists in hugely different environments, artificially or naturally occurring ones across the universe. The phase diagram of crystalline phases of ice is still under construction: a high-pressure phase, ice XIX, has just been reported but its structure remains ambiguous.
Creating predictable, controllable nanoparticles relies on a mechanistic understanding of their synthesis. Here, through integrated in situ liquid microscopy and first-principles calculations, the authors elucidate the atomistic details involved in the formation of colloidal core-shell nanoparticles.
Zirconium-based metal–organic frameworks have defective structures that are useful in catalysis and gas storage. Here, the authors study the interplay between cluster disorder and linker vacancies in PCN-221 and propose a new structure model with tilted Zr6O4(OH)4 clusters rather than Zr8O6 clusters.
The structure of water around Brønsted acid sites in zeolites is shown to influence their catalytic activity. Here the authors shed light on confinement effects in different pores zeolites/water interfaces acidic strength by means of ab-initio molecular dynamics and enhanced sampling metadynamics techniques.
Etching is one of the key considerations in the synthesis, storage, and application of metal nanoparticles. Here, the authors study the etching of water-soluble thiolate-protected gold nanoclusters at a molecular level and reveal an unusual recombination process in the oxidative reaction environment.
Water’s phase diagram exhibits several hydrogen-disordered phases which become ordered upon cooling, but the behavior of ice VI is still debated. The authors, using high-pressure neutron diffraction, identify structural distortions that transform ice VI into ice XIX, here identified as a hydrogen disordered phase.
Precisely controlling the chemical composition and structure of nanoclusters is an ongoing challenge. Here, the authors report a clickable assembly strategy to construct widely varied lanthanide nanoclusters with synergized optical functionalities.
Radiation dosimeters that measure ionizing radiations over a broad range and allow for direct readout are desirable. Here, the authors present a dual-mode photochromic thorium-based metal-organic nanocluster that enables direct visible colorimetric dosimetry of UV, β-ray, and γ-ray radiation.
The primary energy conversion step in photosynthesis, charge separation, takes place in the reaction center. Here the authors investigate the heliobacterial reaction center using multispectral two-dimensional electronic spectroscopy, identifying the primary electron acceptor and revealing the charge separation mechanism.
Nanographenes are emerging as a distinctive class of functional materials for electronic and optical devices. Here, the authors develop a facile strategy to recompose helicenes into a variety of chiral nanographenes through an oxidative cyclo-rearrangement reaction.
Furanose species have a key role in the chemistry of life despite their instability over pyranose ones. The authors, through NMR characterization of the anomeric ratios at equilibrium and a non-equilibrium theoretical treatment, show that a steady temperature gradient, at temperatures relevant to the early Earth, favors furanose over pyranose isomers.
Studying the formation processes of carbon nanodots remains crucial for understanding their properties and chemical structure. Here, the authors investigate the steps involved in their formation process and provide examples for tuning the core-shell design.
The preparation of lanthanide-transition metal clusters containing multiple lanthanide atoms remains challenging. Here, the authors present the controlled on-surface formation of ligand-stabilized heterometallic Ce/Au clusters containing two, three and four Ce atoms bridged by Au adatoms.
Ce(IV) organometallic compounds are rare due to Ce(IV) being a powerful oxidant. Herein, the authors explore the covalency of a pair of organocerium complexes bearing a Ce(IV)-C(aryl) bond and examine their structure by NMR spectroscopy, X-ray diffraction analysis, and computational calculations.
The structures of amorphous MOFs are challenging to characterise. Here the authors use electron microscopy and pair distribution function methods, coupled with a polymerisation-based algorithm to determine the atomic structure of Fe-BTC, demonstrating the power of this computational approach.
Three-body dissociation of water, producing one oxygen and two hydrogen atoms, has been difficult to investigate due to the lack of intense vacuum ultraviolet sources. Here, using a tunable free-electron laser, the authors obtain quantum yields for this channel showing that it is a possible route to prebiotic oxygen formation in interstellar environments.
Studying the nature of actinide-actinide bonds is important for understanding the electronic structure of the 5f elements, but the synthesis of these chemical bonds remains extremely challenging. Here, the authors report a strong covalent Th-Th bond formed between two rarely accessible Th3+ ions, stabilized inside a fullerene cage.
Precise knowledge of chemical composition and atomic structure of functional nanosized systems, such as metal clusters stabilized by an organic molecular layer, allows for detailed computational work to investigate structure-property relations. Here, we discuss selected recent examples of computational work that has advanced understanding of how these clusters work in catalysis, how they interact with biological systems, and how they can make self-assembled, macroscopic materials. A growing challenge is to develop effective new simulation methods that take into account the cluster-environment interactions. These new hybrid methods are likely to contain components from electronic structure theory combined with machine learning algorithms for accelerated evaluations of atom-atom interactions.
Covalent functionalization of single-walled carbon nanotubes with luminescent sp3-defects generally produces a variety of binding configurations and emission wavelengths. The authors propose a base-mediated nucleophilic functionalization approach to selectively achieve configurations for E11* and E11*- or purely E11*- defect emission.
Pauling’s electronegativity scale has a fundamental value and uses accessible thermochemical data, but fails at predicting the bonding behavior for several elements. The authors propose their thermochemical scale based on experimental dissociation energies that provides dimensionless values for the electronegativity and recovers the correct trends throughout the periodic table.
Determining the orientation of nanoscale objects in three-dimensional space has typically required complicated optical setups. Here, the authors develop a simple method to retrieve the 3D orientation of luminescent, lanthanide-doped nanorods from a single-shot emission spectrum.
Methane is abundant in the Universe, is an important energy carrier and a model system for fundamental studies. Here, the authors measure the self-diffusion coefficient of supercritical methane at ambient temperature up to the freezing pressure, and find a different behavior than expected based on previous models.
Understanding ice re-crystallization is key to improve the current cryopreservation technologies. Here, the authors bring together experiments and simulations to unravel the atomistic details of the ice re-crystallization inhibition (IRI) activity of poly(vinyl)alcohol—the most potent biomimetic IRI agent.