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Inorganic and physical chemistry

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.

Featured articles

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.

Article | Open Access | | Nature Communications

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).

Article | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Comment | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Comment | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

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.

Article | Open Access | | Nature Communications

Spin-triplet energy transfer in molecular systems underlies important applications for chemistry and devices. Here, the authors investigate the triplet energy transfer in CdSe quantum dots with varying ZnS shell thicknesses to surface-anchored anthracene molecules and identify a stepwise mechanism mediated by endothermic charge-transfer states.

Article | Open Access | | Nature Communications

Vibrational strong coupling controls the ground-state reactivity of molecules in optical cavities, but the underlying theory is still elusive. The authors analyze a molecular system coupled to a cavity mode and find that the reaction rate is suppressed for a particular cavity frequency, related to the topology of the reaction barrier region, analogously to a solvent caging effect.

Article | Open Access | | Nature Communications

Colloidal CdSe nanocrystals hold great promise in applications due to their tunable optical spectrum. Using hybrid time-dependent density functional theory, the authors show that colloidal CdSe nanocrystals are inherently defective with a low energy spectrum dominated by dark, surface-associated excitations.

Article | Open Access | | Nature Communications

The diffusion of fluids in complex nanoporous geometries represents a challenge for modelling approaches. Here, the authors describe the macroscopic diffusivity of a simple fluid in disordered nanoporous materials by bridging microscopic and mesoscopic dynamics with parameters obtained from simple physical laws.

Article | Open Access | | Nature Communications

Vibronic coupling is a key feature of molecular electronic transitions, but its visualization in real space is an experimental challenge. Here the authors, using scanning tunneling microscopy induced luminescence, resolve the effect of vibronic coupling with different modes on the electron distributions in real space in a single pentacene molecule.

Article | Open Access | | Nature Communications

The coexistence of single-crystallinity with a multidomain morphology is a paradoxical crystallographic phenomenon. Here, the authors introduce a crystallographic morphology never reported before. The single-crystals with a curved and hollow morphology offer opportunities to generate a class of synthetic multidomain crystals.

Article | Open Access | | Nature Communications

Ice-nucleating proteins promote ice formation at high sub-zero temperatures, but the mechanism is still unclear. The authors investigate a model ice-nucleating protein at the air-water interface using vibrational sum frequency generation spectroscopy and simulations, revealing its reorientation at low temperatures, which increases contact with water molecules and promotes their ordering.

Article | Open Access | | Nature Communications

Water ice exhibits several hydrogen-disordered phases that become ordered upon lowering the temperature, but ordering of ice VI, one of the main ice phases, is not well understood. Here the authors identify and structurally refine a partially hydrogen-ordered phase, ice XIX, obtained from ice VI, and observe its transition to its partially hydrogen-ordered sibling ice XV.

Article | Open Access | | Nature Communications

The dissociation mechanism of the heme axial ligand in heme proteins is not yet fully understood. The authors investigate the photodissociation dynamics of the bond between heme Fe and methionine S in ferrous cytochrome c using femtosecond time-resolved X-ray solution scattering and X-ray emission spectroscopy, simultaneously tracking electronic and nuclear structure changes.

Article | Open Access | | Nature Communications

The obtention and study of actinide elements is challenging due to various factors including their radioactivity and scarcity. Herein, the authors characterize the atomic and electronic structure of Am, Cm, Bk, and Cf compounds using a transmission electron microscopy-based workflow that only requires nanogram amounts of the actinide element.

Article | Open Access | | Nature Communications

High-valent metal nitrides are difficult to stabilise due to the high thermodynamic stability and chemical inertness of N2. Here, the authors employ a large volume press to prepare an iron(IV) nitridoferrate Ca4FeIVN4 from Fe2N and Ca3N2 via azide-mediated oxidation under high pressure conditions.

Article | Open Access | | Nature Communications

Warm dense silica is a key component in rocky planets’ mantles, but reproducing the relevant conditions in experiments is challenging. Here the authors use a double-shock technique to achieve such conditions and measure the reflectivity in situ, providing insight into the conductivity and its possible impact on dynamo processes in super-Earths’ mantles.

Article | Open Access | | Nature Communications

The identification of true catalytically active species allows for a better understanding of a catalytic process and its potential improvement. Here, the authors report that the perceived heterogeneous photocatalysis with Bi2O3 in the presence of alkyl bromides involves a homogeneous BinBrm species as the true photocatalyst.

Article | Open Access | | Nature Communications

Despite recent progress in individual nanocluster synthesis, understanding the competing or coexisting effects between particles in solution remains challenging. Here, the authors present the synthesis of a bi-nanocluster system comprising two atomically precise nanoclusters, and map out the interdependent relationship between them.

Article | Open Access | | Nature Communications

Spin polarization is at the basis of quantum information and underlies some natural processes, but many aspects still need to be explored. Here, the authors, by quantum mechanical computations, show that even a weak spin-orbit coupling near a conical intersection can induce large spin selection, with consequences for spin manipulation in photochemical or electrochemical reactions.

Article | Open Access | | Nature Communications

Solid hydrogen has increasingly hindered rotation under high pressure, but the effect on spin isomer populations had not been directly probed. Here the authors measure NMR spectra of solid hydrogen up to the megabar, and observe the crossover to a spin 1/2 dipolar system above 70 GPa where distinction between ortho and para spin isomers is lost.

Article | Open Access | | Nature Communications

Inorganic soft materials are an attractive concept but challenging to make. Here the authors have developed a hydrogel consisting of inorganic nanosheets (14 wt%) and water (86 wt%) that undergoes thermally induced reversible and abrupt changes in its internal structure and mechanical elasticity (23-fold).

Article | Open Access | | Nature Communications

The green component of the solar spectrum can efficiently drive natural photosynthesis, but the process has been little investigated due to the complexity of the excited states involved. Here the authors utilize polarization-dependent two-dimensional electronic-vibrational spectroscopy to define the origin and dynamics of these states in light-harvesting complex II.

Article | Open Access | | Nature Communications

There currently exists some debate as to exact mechanism of cation exchange in semiconductor nanocrystals, a crucial question regarding the fundamental materials chemistry of these systems. Here, the authors report a detailed investigation of the mechanism of cation exchange in nanocrystals, which unambiguously shows evidence of interstitial intermediates during the exchange process.

Article | Open Access | | Nature Communications

Unlike traditional chiral metal complexes, which typically contain chiral ligands, in chiral-at-metal complexes chirality originates from a stereogenic metal center bound to achiral ligands. Herein, the authors use an unsymmetric tridentate ligand to construct a Werner-type tetrahedral chiral-at-zinc complex which displays high configurational stability and catalyzes an oxa-Diels-Alder reaction with high yield and enantioselectivity.

Article | Open Access | | Nature Communications