Focus |

# Inorganic, Nanoscale and Physical Chemistry

Jacilynn Brant: materials chemistry and functional materials.

Long Chen: photo- and heterogeneous catalysis.

Margherita Citroni: physical and analytical chemistry.

Ariane Vartanian: nanoscale and supramolecular chemistry.

Welcome to the Nature Communications Editors’ Highlights webpage on inorganic, nanoscale and physical chemistry. Each month our editors select a small number of Articles recently published in Nature Communications that they believe are particularly interesting or important.

The aim is to provide a snapshot of some of the most exciting work published in the area of inorganic, nanoscale and physical chemistry at Nature Communications.

Make sure to check the Editors' Highlights page each month for new featured articles.

# Jacilynn Brant

### A solvent-assisted ligand exchange approach enables metal-organic frameworks with diverse and complex architectures

Metal-organic frameworks are promising for a range of applications, but architectural control is challenging. Here the authors use solvent-assisted ligand exchange to access a variety of metal-organic framework nanomaterials for precursors of nanoporous carbon with sodium ion storage properties.

Article | Open Access | | Nature Communications

### Insulated conjugated bimetallopolymer with sigmoidal response by dual self-controlling system as a biomimetic material

Molecules can serve as biomimetic sensors, but dual self-controlling systems that involve self-activation and self-regulation are difficult to mimic. Here the authors report an insulated conjugated bimetallopolymer with cooperative multiple transition metals that phosphoresces in response to carbon monoxide.

Article | Open Access | | Nature Communications

### Controlled release of H2S and NO gases through CO2-stimulated anion exchange

Solid materials releasing gas molecules under external stimuli usually require external energy for reliable operation. Here the authors synthesize layered double hydroxides for the autonomous release of H2S and NO gases in response to CO2-stimulus.

Article | Open Access | | Nature Communications

### Cation-induced chirality in a bifunctional metal-organic framework for quantitative enantioselective recognition

Metal-organic frameworks with luminescence and chirality are promising for luminescent sensors for chiral molecules. Here, the authors use cation exchange to introduce chirality in multifunctional metal-organic framework systems for rapid enantioselective luminescent sensing.

Article | Open Access | | Nature Communications

### Giant anisotropic thermal expansion actuated by thermodynamically assisted reorientation of imidazoliums in a single crystal

Designing materials with large thermal expansion is highly desirable to fabricate microscale devices. The authors report unusually large anisotropic negative and positive thermal expansion in a simple crystalline material, through temperature-driven orientation of imidazole cations acting as molecular wheels.

Article | Open Access | | Nature Communications

### Two-dimensional electronic spectroscopy reveals liquid-like lineshape dynamics in CsPbI3 perovskite nanocrystals

Lead-halide perovskites have promising optoelectronic properties, determined by interplay of electronic and structural properties. Here the authors probe CsPbI3 nanocrystals by two-dimensional electronic spectroscopy, showing liquid-like structural dynamics signature of polaron formation.

Article | Open Access | | Nature Communications

### Carbon dioxide capture and efficient fixation in a dynamic porous coordination polymer

Porous coordination polymers that possess structural flexibility show great promise for gas adsorption and catalysis. Here the authors synthesize a dynamic porous coordination polymer with rotating ligands that permit effective CO2 trapping, and demonstrate subsequent CO2 cycloaddition to epoxides.

Article | Open Access | | Nature Communications

### Integration of mesopores and crystal defects in metal-organic frameworks via templated electrosynthesis

Incorporating mesopores and active sites into metal-organic framework materials has proven advantageous for their catalytic application, but remains challenging to achieve. Here the authors obtain mesoporous, defect-rich metal-organic frameworks through templated electrosynthesis using ionic liquids as both electrolyte and template.

Article | Open Access | | Nature Communications

### Hydrogen-bonded frameworks for molecular structure determination

Single crystal X-ray diffraction is an invaluable tool for molecular structure determination, but growing single crystals is often an arduous process. Here the authors find that the structures of a wide array of molecules can be determined by SCXRD when included in hydrogen-bonded guanidinium organosulfonate host frameworks in a single-step crystallization.

Article | Open Access | | Nature Communications

### Quadruple bonding between iron and boron in the BFe(CO)3− complex

While main group elements possess four valence orbitals that are accessible for bonding, quadruple bonding to main group elements is very rarely observed. Here the authors report that boron is able to form four bonding interactions with iron in the BFe(CO)3- anion complex.

Article | Open Access | | Nature Communications

# Long Chen

### Palladium-bearing intermetallic electride as an efficient and stable catalyst for Suzuki cross-coupling reactions

In Suzuki coupling reactions, excellent catalytic performance require negatively charged Pd species and the avoidance of metal leaching or clustering. Here the authors implanted Pd sites into an intermetallic electride, Y3Pd2, which serves as an efficient and stable catalyst for Suzuki coupling reactions.

Article | Open Access | | Nature Communications

### Acidity enhancement through synergy of penta- and tetra-coordinated aluminum species in amorphous silica networks

Increasing the strength of silanols in silica-aluminas can promote their catalytic activity in various applications. Here, the authors present a synergistic effect of two neighboring Al sites on the same silanol group, which can enhance the strength of silanol proton from moderate to zeolitic strength.

Article | Open Access | | Nature Communications

### Ultrastable Au nanoparticles on titania through an encapsulation strategy under oxidative atmosphere

Sintering-resistant Au nanoparticles are highly desirable due to their low Tammann temperature. Here, the authors report an ultrastable titania-supported Au nanocatalyst through an encapsulation strategy under oxidative atmosphere.

Article | Open Access | | Nature Communications

### Platinum–copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis

Selective hydrogenolysis of biomass glycerol to propanediol is a promising route for the production of high-value chemicals but remains a challenge. Here, the authors find a PtCu single atom alloy catalyst exhibits remarkably boosted performance with a turnover frequency value of 2.6 × 103 molglycerol·molPtCu–SAA−1·h−1.

Article | Open Access | | Nature Communications

### Unassisted solar lignin valorisation using a compartmented photo-electro-biochemical cell

The effective valorisation of lignin is crucial for realizing a sustainable biorefinery. Here, the authors report that a compartmented photo-electro-biochemical design enables unassisted, selective, and stable solar lignin valorisation without the need for any additional bias or chemicals.

Article | Open Access | | Nature Communications

### Near 100% CO selectivity in nanoscaled iron-based oxygen carriers for chemical looping methane partial oxidation

Chemical looping methane partial oxidation is an effective technology to produce syngas with a minimal energy penalty. Here, the authors design and develop a mesoporous silica supported nanoparticle oxygen carrier that enables a near 100% CO generation with high recyclability and substantially lower operating temperature.

Article | Open Access | | Nature Communications

### Interfacial Fe5C2-Cu catalysts toward low-pressure syngas conversion to long-chain alcohols

Long-chain alcohols synthesis from syngas conversion is a promising route for the production of high-value chemicals. Here the authors show that a heterogeneous Fe5C2/Cu catalyst derived from layered double hydroxides precursor exhibits excellent performance with a space time yield of 0.101 g gcat−1 h−1 at a low pressure of 1 MPa.

Article | Open Access | | Nature Communications

### A nanofluidic device for parallel single nanoparticle catalysis in solution

Single nanoparticle catalysis studies enable structure–function correlations beyond averaged properties. Here, the authors present a versatile nanofluidics- and fluorescence-based platform for highly parallelized single particle catalysis in solution.

Article | Open Access | | Nature Communications

### Unraveling the coordination structure-performance relationship in Pt1/Fe2O3 single-atom catalyst

In single-atom catalysts (SACs), little is known about how the coordination structure of single atoms affects the catalytic performance. Here, the authors discover that in Pt1/Fe2O3 SAC, the coordination number of the first shell Pt-O is well correlated with the Pt electronic property and the hydrogenation activity.

Article | Open Access | | Nature Communications

### Dopant-tuned stabilization of intermediates promotes electrosynthesis of valuable C3 products

The electro-oxidative synthesis of valued chemicals offers to enhance the overall efficiency and economic viability of renewable electrosynthesis systems. Here, the authors use dopant-tuned catalysts to promote the electrosynthesis of dimethyl carbonate from CO and methanol via oxidative carbonylation.

Article | Open Access | | Nature Communications

# Margherita Citroni

### Confined water-mediated high proton conduction in hydrophobic channel of a synthetic nanotube

Water confined in natural or synthetic hydrophobic nano-spaces behaves differently than in the bulk. Here the authors investigate water in hydrophobic synthetic 1D nanochannels revealing water clustering in tetramers and octamers and high proton conductivity, along with a continuous liquid to solid transition.

Article | Open Access | | Nature Communications

### Vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering

Photoinduced non-adiabatic intramolecular processes have important applications but their mechanisms are challenging to explore. Here the authors detect and assign vibrational wavepacket dynamics in a Fe carbene complex by ultrafast X-ray emission spectroscopy and X-ray scattering, resolving nuclear and electronic motion.

Article | Open Access | | Nature Communications

### Ice Ic without stacking disorder by evacuating hydrogen from hydrogen hydrate

Metastable cubic ice has been identified in several conditions relevant to geo and astrochemistry, but was always characterized by stacking disorder. Here the authors synthesize a hydrogen hydrate and degas hydrogen, obtaining pure non-defected cubic ice, observed by X-ray and neutron diffraction.

Article | Open Access | | Nature Communications

### Ultrafast shock synthesis of nanocarbon from a liquid precursor

Carbon nanomaterials have widespread application but fundamental aspects of their formation are still unclear. Here the authors explore the shock-induced synthesis of carbon nanoallotropes from liquid CO by time-resolved reflectivity and computations identifying the growth mechanism at the sub-nanosecond timescale

Article | Open Access | | Nature Communications

### Feshbach resonances in the F + H2O → HF + OH reaction

Feshbach resonances are transiently trapped states along a reaction coordinate, providing a probe to the reaction’s potential energy surface (PES) but difficult to analyze in polyatomic systems. Here the authors identify Feshbach resonances in a reacting 4-atom system by state-to-state quantum dynamics using a full-dimensional PES.

Article | Open Access | | Nature Communications

### Strong inverse kinetic isotope effect observed in ammonia charge exchange reactions

Inverse kinetic isotope effects (KIEs) are rarely observed. Here, the authors report an inverse KIE in the charge transfer reaction of $${{\rm{Xe}}}^{+}$$$Xe+$ with ammonia. $${{\rm{ND}}}_{3}$$$ND3$ reacts more than 3 times faster than $${{\rm{NH}}}_{3}$$$NH3$, despite no N-H or N-D bonds being broken, with implications for our understanding of interstellar chemistry.

Article | Open Access | | Nature Communications

### Ultrafast valence to non-valence excited state dynamics in a common anionic chromophore

Photoactive biomolecules rely on chromophores whose photochemistry depends on the environment. Here, the excited state dynamics of a model for the anionic biochromophore in photoactive yellow protein is investigated by time-resolved photoelectron spectroscopy showing involvement of a non-valence state, and lack of E-Z isomerisation in the gas phase.

Article | Open Access | | Nature Communications

### Vibronic coherence evolution in multidimensional ultrafast photochemical processes

Energy transfer in light harvesting complexes involves electronic, vibrational, and vibronic couplings which are challenging to resolve. Here the authors observe the time-evolution of vibronic coherences driving charge transfer in a photoexcited solvated transition metal complex by two- and three-dimensional electronic-vibrational spectroscopy.

Article | Open Access | | Nature Communications

### Combined orbital tomography study of multi-configurational molecular adsorbate systems

The shape and energy of frontier orbitals determine the reactivity of molecular systems. Combining orbital tomography based on photoelectron spectroscopy with electron diffraction and DFT, the authors investigate a complex multi-configurational adsorbate system revealing adsorptions geometries and hierarchy and geometry of molecular orbitals.

Article | Open Access | | Nature Communications

### Oxygen-catalysed sequential singlet fission

Singlet fission is a promising carrier multiplication process, where a singlet exciton is split in two triplet states. Here the authors propose an oxygen-assisted two-step mechanism for singlet fission accounting for ~ 40% triplet quantum yield in dilute solutions where the single-step mechanism is inactive.

Article | Open Access | | Nature Communications

# Ariane Vartanian

### Self-assembled conjoined-cages

Developing simple routes for construction of multi-compartmental cages is a compelling and challenging task. Here, the authors report modular construction of multi-3D-cavity cages featuring one, two or three units of a [Pd2L4] entity conjoined with a [Pd3L6] core.

Article | Open Access | | Nature Communications

### Weak functional group interactions revealed through metal-free active template rotaxane synthesis

Weak interactions between functional groups are often difficult to characterize in host–guest complexes. Here, the authors report the metal-free active template synthesis of a series of rotaxanes that permit a range of kinetically stabilized, weak crown ether-axle interactions to be characterized in solution and the solid state.

Article | Open Access | | Nature Communications

### Atomically resolved Au52Cu72(SR)55 nanoalloy reveals Marks decahedron truncation and Penrose tiling surface

The formation of Marks truncated decahedra in nanoparticles is ubiquitous but the mechanism has not been fully understood. Here, the authors provide atomic-level insights by creating a non-truncated Au52Cu72(SR)55 decahedral nanocluster and comparing it with the truncated homogold decahedra.

Article | Open Access | | Nature Communications

### Emergence of chirality and structural complexity in single crystals at the molecular and morphological levels

Single crystallinity combined with multidomain morphology is counterintuitive. Here, the authors achieve such a phenomenon in a metal-organic framework that also displays chirality at both the molecular and morphological levels.

Article | Open Access | | Nature Communications

### A metal–peptide capsule by multiple ring threading

Constructing molecular cages from entangled molecules is a complex task requiring precise topological control. Here, the authors thread together six metal-peptide rings into a giant cubic molecular capsule with a defined cavity and 24 crossover points.

Article | Open Access | | Nature Communications

### Colloidal quantum dot molecules manifesting quantum coupling at room temperature

In analogy to the coupling of atoms into molecules, the authors fuse colloidal semiconductor nanocrystals into quantum dot dimers. These nanocrystal ‘molecules’ exhibit significant quantum coupling effects, making them promising for applications in devices and potential quantum technologies.

Article | Open Access | | Nature Communications

### Unveiling how intramolecular stacking modes of covalently linked dimers dictate photoswitching properties

Covalently bridged π-stacked dimers are excellent molecular platforms for understanding the relationship between stacking orientation and properties. Here, the authors synthesize a pair of π-stacked dimers that are aligned either cofacially or crosswise, allowing them to compare how the intramolecular stacking mode affects each dimer’s photoswitching properties.

Article | Open Access | | Nature Communications

### Template-controlled on-surface synthesis of a lanthanide supernaphthalocyanine and its open-chain polycyanine counterpart

Extending the π‐conjugation of phthalocyanine dyes, while synthetically challenging, has the potential to produce desirable new molecular materials. Here, the authors use a templated on‐surface approach to synthesize several extended phthalocyanine derivatives from the same building block, including a lanthanide superphthalocyanine and an open‐chain polycyanine.

Article | Open Access | | Nature Communications

### How to control single-molecule rotation

The orientation of a molecule on a surface affects many processes, so the ability to control single-molecule rotation could be powerful. Here, the authors use the electric field from a scanning tunneling microscope tip to precisely induce unidirectional rotation of a polar molecule, allowing visualization of the molecule’s internal dipole moment.

Article | Open Access | | Nature Communications

### Direct imaging of light-element impurities in graphene reveals triple-coordinated oxygen

Annular dark field scanning transmission electron microscopy is able to distinguish the contrasts between light elements. Here, the authors directly image the bonding configurations of oxygen and nitrogen atoms in defective graphene, and surprisingly identify instances of unusual triple-coordinated oxygen with three carbon neighbors.

Article | Open Access | | Nature Communications