Inorganic and physical chemistry

Self-regulated co-assembly of soft and hard nanoparticles

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.

Yan Cui,
Hongyan Zhu ⋯
Huibin Qiu

Article | Open Access | 28 Sep 2021 | Nature Communications

Breaking a dative bond with mechanical forces

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.

Pengcheng Chen,
Dingxin Fan ⋯
Nan Yao

Article | Open Access | 24 Sep 2021 | Nature Communications

Filming ultrafast roaming-mediated isomerization of bismuth triiodide in solution

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…

Eun Hyuk Choi,
Jong Goo Kim ⋯
Hyotcherl Ihee

Article | Open Access | 5 Aug 2021 | Nature Communications

Pentaphosphaferrocene-mediated synthesis of asymmetric organo-phosphines starting from white phosphorus

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…

Stephan Reichl,
Eric Mädl ⋯
Manfred Scheer

Article | Open Access | 1 Oct 2021 | Nature Communications

Conformer-specific polar cycloaddition of dibromobutadiene with trapped propene ions

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…

Ardita Kilaj,
Jia Wang ⋯
Stefan Willitsch

Article | Open Access | 18 Oct 2021 | Nature Communications

Two-dimensional monolayer salt nanostructures can spontaneously aggregate rather than dissolve in dilute aqueous solutions

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…

Wenhui Zhao,
Yunxiang Sun ⋯
Xiao Cheng Zeng

Article | Open Access | 23 Sep 2021 | Nature Communications

Access to cationic polyhedral carboranes via dynamic cage surgery with N-heterocyclic carbenes

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…

Jan Vrána,
Josef Holub ⋯
Aleš Růžička

Article | Open Access | 17 Aug 2021 | Nature Communications

Exceptional uranium(VI)-nitride triple bond covalency from 15N nuclear magnetic resonance spectroscopy and quantum chemical analysis

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…

Jingzhen Du,
John A. Seed ⋯
Stephen T. Liddle

Article | Open Access | 24 Sep 2021 | Nature Communications

A hybrid molecular peapod of sp2- and sp3-nanocarbons enabling ultrafast terahertz rotations

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…

Taisuke Matsuno,
Seiya Terasaki ⋯
Hiroyuki Isobe

Article | Open Access | 25 Aug 2021 | Nature Communications

Carbon clusters formed from shocked benzene

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…

D. M. Dattelbaum,
E. B. Watkins ⋯
R. L. Sandberg

Article | Open Access | 1 Sep 2021 | Nature Communications

Methyl groups as widespread Lewis bases in noncovalent interactions

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…

Oliver Loveday &
Jorge Echeverría

Article | Open Access | 19 Aug 2021 | Nature Communications

Rotational and nuclear-spin level dependent photodissociation dynamics of H2S

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,…

Yarui Zhao,
Zijie Luo ⋯
Xueming Yang

Article | Open Access | 22 Jul 2021 | Nature Communications

Liquid flow reversibly creates a macroscopic surface charge gradient

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…

Patrick Ober,
Willem Q. Boon ⋯
Mischa Bonn

Article | Open Access | 2 Jul 2021 | Nature Communications

Machine learning based energy-free structure predictions of molecules, transition states, and solids

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.

Dominik Lemm,
Guido Falk von Rudorff &
O. Anatole von Lilienfeld

Article | Open Access | 22 Jul 2021 | Nature Communications

A curved host and second guest cooperatively inhibit the dynamic motion of corannulene

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,…

Yang Yang,
Tanya K. Ronson ⋯
Jonathan R. Nitschke

Article | Open Access | 2 Jul 2021 | Nature Communications

Self-assembly of N-heterocyclic carbenes on Au(111)

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…

Alex Inayeh,
Ryan R. K. Groome ⋯
Alastair B. McLean

Article | Open Access | 29 Jun 2021 | Nature Communications

Anomalous formation of trihydrogen cations from water on nanoparticles

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…

M. Said Alghabra,
Rami Ali ⋯
Ali S. Alnaser

Article | Open Access | 22 Jun 2021 | Nature Communications

Photon upconversion through triplet exciton-mediated energy relay

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…

Sanyang Han,
Zhigao Yi ⋯
Xiaogang Liu

Article | Open Access | 17 Jun 2021 | Nature Communications

The everlasting hunt for new ice phases

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.

Thomas C. Hansen

Comment | Open Access | 26 May 2021 | Nature Communications

Atomistic insights into the nucleation and growth of platinum on palladium nanocrystals

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…

Wenpei Gao,
Ahmed O. Elnabawy ⋯
Miaofang Chi

Article | Open Access | 2 Jun 2021 | Nature Communications

Understanding disorder and linker deficiency in porphyrinic zirconium-based metal–organic frameworks by resolving the Zr8O6 cluster conundrum in PCN-221

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…

Charlotte Koschnick,
Robert Stäglich ⋯
Bettina V. Lotsch

Article | Open Access | 25 May 2021 | Nature Communications

Confinement effects and acid strength in zeolites

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…

Emanuele Grifoni,
GiovanniMaria Piccini ⋯
Michele Parrinello

Article | Open Access | 11 May 2021 | Nature Communications

Revealing the etching process of water-soluble Au25 nanoclusters at the molecular level

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…

Yitao Cao,
Tongyu Liu ⋯
Jianping Xie

Article | Open Access | 28 May 2021 | Nature Communications

Structure and nature of ice XIX

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…

Christoph G. Salzmann,
John S. Loveday ⋯
Craig L. Bull

Article | Open Access | 26 May 2021 | Nature Communications

A luminescent view of the clickable assembly of LnF3 nanoclusters

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.

Jie Zhou,
Yang Wei ⋯
Ling Huang

Article | Open Access | 19 May 2021 | Nature Communications

Visible colorimetric dosimetry of UV and ionizing radiations by a dual-module photochromic nanocluster

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.

Huangjie Lu,
Jian Xie ⋯
Jian Lin

Article | Open Access | 14 May 2021 | Nature Communications

Excitonic structure and charge separation in the heliobacterial reaction center probed by multispectral multidimensional spectroscopy

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…

Yin Song,
Riley Sechrist ⋯
Jennifer P. Ogilvie

Article | Open Access | 14 May 2021 | Nature Communications

Oxidative cyclo-rearrangement of helicenes into chiral nanographenes

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.

Chengshuo Shen,
Guoli Zhang ⋯
Huibin Qiu

Article | Open Access | 13 May 2021 | Nature Communications

Equilibrium and non-equilibrium furanose selection in the ribose isomerisation network

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…

Avinash Vicholous Dass,
Thomas Georgelin ⋯
Francesco Piazza

Article | Open Access | 12 May 2021 | Nature Communications

Snapshots into carbon dots formation through a combined spectroscopic approach

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.

Francesco Rigodanza,
Max Burian ⋯
Maurizio Prato

Article | Open Access | 11 May 2021 | Nature Communications

On-surface preparation of coordinated lanthanide-transition-metal clusters

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.

Jing Liu,
Jie Li ⋯
Yongfeng Wang

Article | Open Access | 12 Mar 2021 | Nature Communications

Isolation and characterization of a covalent CeIV-Aryl complex with an anomalous 13C chemical shift

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.

Grace B. Panetti,
Dumitru-Claudiu Sergentu ⋯
Eric J. Schelter

Article | Open Access | 17 Mar 2021 | Nature Communications

Mixed hierarchical local structure in a disordered metal–organic framework

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.

Adam F. Sapnik,
Irene Bechis ⋯
Thomas D. Bennett

Article | Open Access | 6 Apr 2021 | Nature Communications

Three body photodissociation of the water molecule and its implications for prebiotic oxygen production

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…

Yao Chang,
Yong Yu ⋯
Xueming Yang

Article | Open Access | 30 Apr 2021 | Nature Communications

Characterization of a strong covalent Th3+–Th3+ bond inside an Ih(7)-C80 fullerene cage

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…

Jiaxin Zhuang,
Roser Morales-Martínez ⋯
Ning Chen

Article | Open Access | 22 Apr 2021 | Nature Communications

Prospects and challenges for computer simulations of monolayer-protected metal clusters

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…

Sami Malola &
Hannu Häkkinen

Comment | Open Access | 13 Apr 2021 | Nature Communications

Synthetic control over the binding configuration of luminescent sp3-defects in single-walled carbon nanotubes

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…

Simon Settele,
Felix J. Berger ⋯
Jana Zaumseil

Article | Open Access | 9 Apr 2021 | Nature Communications

Thermochemical electronegativities of the elements

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…

Christian Tantardini &
Artem R. Oganov

Article | Open Access | 7 Apr 2021 | Nature Communications

Measuring 3D orientation of nanocrystals via polarized luminescence of rare-earth dopants

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.

Jeongmo Kim,
Reinaldo Chacón ⋯
Thierry Gacoin

Article | Open Access | 29 Mar 2021 | Nature Communications

Diffusion in dense supercritical methane from quasi-elastic neutron scattering measurements

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…

Umbertoluca Ranieri,
Stefan Klotz ⋯
Livia E. Bove

Article | Open Access | 30 Mar 2021 | Nature Communications

The atomistic details of the ice recrystallisation inhibition activity of PVA

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…

Fabienne Bachtiger,
Thomas R. Congdon ⋯
Gabriele C. Sosso

Article | Open Access | 26 Feb 2021 | Nature Communications

Stereoselectivity in spontaneous assembly of rolled incommensurate carbon bilayers

Incommensurate pairing is a type of stereoisomerism, observed in carbon bilayers, that arises from the twisted orientations of the graphitic layers. Here, the authors create a finite molecular version of an incommensurate carbon bilayer in the form of two…

Taisuke Matsuno,
Yutaro Ohtomo ⋯
Hiroyuki Isobe

Article | Open Access | 10 Mar 2021 | Nature Communications

Shallow distance-dependent triplet energy migration mediated by endothermic charge-transfer

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…

Runchen Lai,
Yangyi Liu ⋯
Kaifeng Wu

Article | Open Access | 9 Mar 2021 | Nature Communications

Cavity frequency-dependent theory for vibrational polariton chemistry

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…

Xinyang Li,
Arkajit Mandal &
Pengfei Huo

Article | Open Access | 26 Feb 2021 | Nature Communications

Colloidal CdSe nanocrystals are inherently defective

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…

Tamar Goldzak,
Alexandra R. McIsaac &
Troy Van Voorhis

Article | Open Access | 9 Feb 2021 | Nature Communications

Bridging scales in disordered porous media by mapping molecular dynamics onto intermittent Brownian motion

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…

Colin Bousige,
Pierre Levitz &
Benoit Coasne

Article | Open Access | 15 Feb 2021 | Nature Communications

A tris-spiro metalla-aromatic system featuring Craig-Möbius aromaticity

Spiroaromatic compounds are advantageous platforms for designing expanded aromatic systems. Herein, the authors present a tris‐spiro metalla‐aromatic Vanadium compound which forms a 40π Craig‐Möbius aromatic system.

Zhe Huang,
Yongliang Zhang ⋯
Zhenfeng Xi

Article | Open Access | 26 Feb 2021 | Nature Communications

Probing intramolecular vibronic coupling through vibronic-state imaging

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…

Fan-Fang Kong,
Xiao-Jun Tian ⋯
J. G. Hou

Article | Open Access | 24 Feb 2021 | Nature Communications

Molecular cannibalism: Sacrificial materials as precursors for hollow and multidomain single crystals

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…

Maria Chiara di Gregorio,
Merna Elsousou ⋯
Milko E. van der Boom

Article | Open Access | 11 Feb 2021 | Nature Communications

Ice-nucleating proteins are activated by low temperatures to control the structure of interfacial water

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…

Steven J. Roeters,
Thaddeus W. Golbek ⋯
Tobias Weidner

Article | Open Access | 19 Feb 2021 | Nature Communications

Inorganic and physical chemistry

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