Nanoscale materials articles within Nature Chemistry

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  • Article
    | Open Access

    The insertion of metal atoms and heteroaromatic units provides a way to tune the optical, electronic and magnetic properties of graphene nanoribbons. Now the synthesis of a porphyrin-fused graphene nanoribbon with a narrow bandgap and high charge mobility has been achieved, and this material used to fabricate field-effect and single-electron transistors.

    • Qiang Chen
    • , Alessandro Lodi
    •  & Harry L. Anderson
  • Article |

    The design of open-shell nanographenes is commonly limited to systems featuring a single magnetic origin. Now a strategy that combines topological frustration and electron–electron interactions has been developed to generate a butterfly-shaped nanographene that hosts four highly entangled π-spins and exhibits both ferromagnetic and anti-ferromagnetic coupling.

    • Shaotang Song
    • , Andrés Pinar Solé
    •  & Jiong Lu
  • Article
    | Open Access

    Switching the magnetic state of a polycyclic conjugated hydrocarbon in a reversible and controlled manner is challenging. Now, by means of single-molecule scanning probe microscopy, an indenofluorene isomer on ultrathin NaCl films has been shown to adopt both open- and closed-shell states. Furthermore, bidirectional switching between the two states is achieved by changing the adsorption site of the molecule.

    • Shantanu Mishra
    • , Manuel Vilas-Varela
    •  & Leo Gross
  • Article
    | Open Access

    Enzyme-initiated polymerization-induced self-assembly has been used to generate various biomimetic structures. Now, myoglobin’s activity is used for biocatalytic polymerization-induced self-assembly to generate vesicular artificial cells. As various cargoes can be encapsulated during polymerization, these artificial cells are capable of protein expression and can act as microreactors for distinct enzymatic reactions.

    • Andrea Belluati
    • , Sètuhn Jimaja
    •  & Nico Bruns
  • Article |

    The synthesis of two-dimensional (2D) organic lateral heterostructures with desirable properties from organic single crystals remains challenging. Now, 2D organic lateral heterostructures have been produced by using a liquid-phase growth approach and vapour-phase growth method, enabling the structural inversion of organic lateral heterostructures via a two-step strategy.

    • Qiang Lv
    • , Xue-Dong Wang
    •  & Liang-Sheng Liao
  • Article |

    The physicochemical driving forces of protein-free, RNA-driven phase transitions were previously unclear, but it is now shown that RNAs undergo entropically driven liquid–liquid phase separation upon heating in the presence of magnesium ions. In the condensed phase, RNAs can undergo an enthalpically favourable percolation transition that leads to arrested condensates.

    • Gable M. Wadsworth
    • , Walter J. Zahurancik
    •  & Priya R. Banerjee
  • Article
    | Open Access

    Molecular systems with coincident cyclic and superhelical symmetry axes have considerable advantages for materials design as they can be lengthened or shortened by changing the length of the monomers. Now a systematic approach to generate modular repeat protein oligomers with combined symmetry that can be extended by repeat propagation has been developed.

    • Neville P. Bethel
    • , Andrew J. Borst
    •  & David Baker
  • Article |

    Two-dimensional hybrid perovskites have gained substantial interest recently due to their controllable optoelectronic properties; however precise control over layer thickness has been synthetically challenging. Now a crystal growth method is shown to achieve high-quality single crystals of organic semiconductor-incorporated perovskites with control over their thickness and length through judicious solvent choice, affording precisely tuned optoelectronic properties.

    • Jee Yung Park
    • , Ruyi Song
    •  & Letian Dou
  • Article |

    Functionalizing two-dimensional transition-metal carbide (MXene) surfaces can alter their properties, but covalent functionalization has been synthetically challenging. Now, it has been shown that various organic groups can be covalently attached to MXene surfaces through amido and imido bonds. The resulting hybrid organic–inorganic structures exhibit Fano resonances and superior stability compared with traditional MXenes with a mixture of –F, –O and –OH surface terminations.

    • Chenkun Zhou
    • , Di Wang
    •  & Dmitri V. Talapin
  • Article |

    Visualizing single-molecule reactions using electron microscopy can be difficult because of potential radiation damage from the electron beam. Now, however, it has been shown that a high-energy electron beam can be used to synthesize metallo-azafullerenes. Atomic-resolution, time-resolved transmission electron microscopy, with the help of computational calculations, is used to monitor the metal-encapsulation dynamics.

    • Helen Hoelzel
    • , Sol Lee
    •  & Dominik Lungerich
  • Article |

    Hybrid structures made up of quantum dots functionalized with molecules are highly tunable platforms for light-driven applications; however, the interaction between their components is often weak. Now it has been shown that by connecting molecules to silicon quantum dots via p-conjugated tethers, strongly coupled exciton states can be generated that prove advantageous for photon upconversion.

    • Kefu Wang
    • , R. Peyton Cline
    •  & Ming Lee Tang
  • Article |

    Clathrates—open crystals with a hierarchy of polyhedral cages—are mostly found in atomic and molecular systems. Now, it has been shown through Monte Carlo simulations that the formation of colloidal host–guest clathrates can be driven by entropy alone, through entropy compartmentalization.

    • Sangmin Lee
    • , Thi Vo
    •  & Sharon C. Glotzer
  • News & Views |

    Systems that feature long-range order but no translational periodicity are intriguing. Now, a T-shaped molecule consisting of three non-miscible components has been devised that self-assembles into a columnar liquid quasicrystal.

    • Marianne Impéror-Clerc
  • Article |

    Large biomolecules cannot be loaded into conventional Janus nanoparticles with small mesopores, preventing the establishment of efficient logic-gate systems in single Janus nanoparticles. Now, an emulsion-oriented assembly approach has been shown to fabricate Janus double-spherical nanoparticles with dual-tunable mesopores, enabling the design of various single-particle-level logic systems.

    • Tiancong Zhao
    • , Liang Chen
    •  & Dongyuan Zhao
  • Article |

    Covalent organic frameworks (COFs) have remained difficult to grow as single crystals. Now, amphiphilic amino-acid derivatives that assemble in micelles in aqueous solutions have been shown to promote the growth of a variety of imine-bridged COFs into single crystals, in a step-by-step fashion, within their hydrophobic compartment.

    • Zhipeng Zhou
    • , Lei Zhang
    •  & Zhikun Zheng
  • Article |

    Quasicrystals are intriguing structures that exhibit long-range positional correlations but no periodicity in real space. Now, T-shaped amphiphilic molecules featuring rigid cores have been found to self-assemble into a columnar liquid quasicrystal with dodecagonal symmetry. The honeycomb structure observed arises from a strictly quasiperiodic tessellation of square, triangular and trapezoidal tiles, rather than from random tiling.

    • Xiangbing Zeng
    • , Benjamin Glettner
    •  & Carsten Tschierske
  • Article |

    Current strategies for photoinduced olefin metathesis lack wavelength tunability. Now, plasmonic nanoparticles have been used to activate latent ruthenium catalysts, enabling light-induced olefin metathesis in the infrared range with several advantages when compared with conventional heating. Implementing this approach in ring-opening metathesis polymerization resulted in photoresponsive polymer–nanoparticle composites with enhanced mechanical properties.

    • Nir Lemcoff
    • , Noy B. Nechmad
    •  & Yossi Weizmann
  • News & Views |

    An organic quantum magnet has been prepared in short chains of porphyrin derivatives through a combination of on-surface synthesis and atom manipulation using the tip of a scanning probe microscope.

    • P. Jelínek
  • Article |

    Gold nanoparticles typically exhibit hard-sphere-like assembly behaviour, but now the size, morphology and symmetry of crystals of Au25 nanoparticles have been tuned. The presence of excess tetraethylammonium cations has been shown to promote the one-dimensional assembly of the nanoparticles, which in turn form rod-like crystals, by stabilizing dynamically detached ligands from adjacent particles into interparticle linkers through CH⋯π and ion-pairing interactions.

    • Qiaofeng Yao
    • , Lingmei Liu
    •  & Jianping Xie
  • Article
    | Open Access

    Incorporating silicon into organic molecules and materials leads to interesting changes in electronic structure and properties; silabenzenes are attractive species for this purpose, but their high reactivity in solution poses challenges. Now, 1D and 2D covalent organic frameworks featuring disilabenzene rings (C4Si2) as linkers have been prepared by reacting silicon atoms and polyaromatic hydrocarbon precursors on a Au(111) surface.

    • Kewei Sun
    • , Orlando J. Silveira
    •  & Shigeki Kawai
  • Article |

    Identifying and quantifying the biodistribution of synthetic polymeric nanoparticles in biological milieu is crucial for biomedical applications. Now, it has been shown that encoded polymeric amphiphiles with discrete molar masses undergo sequence- and length-dependent self-assembly into precise digital micelles that can be used in direct sequence reading and ex vivo label-free quantification assays.

    • Qiangqiang Shi
    • , Hao Yin
    •  & Shiyong Liu
  • Article |

    Peptide design remains a challenge owing to the large library of amino acids. Rational design approaches, although successful, result in a peptide design bias. Now it has been shown that AI techniques can be used to overcome such bias and discover unusual peptides as efficiently as humans.

    • Rohit Batra
    • , Troy D. Loeffler
    •  & Subramanian K. R. S. Sankaranarayanan
  • Article |

    Quantum nanomagnets, which display collective quantum behaviours, serve as important components in modern quantum technologies, but their fabrication has remained challenging. Quantum nanomagnets have now been constructed spin by spin in metal-free porphyrin chains, using on-surface synthesis and hydrogen manipulation using a scanning tunnelling microscope, and their collective quantum behaviours have been clearly resolved.

    • Yan Zhao
    • , Kaiyue Jiang
    •  & Shiyong Wang
  • Article
    | Open Access

    On-surface synthesis enables highly reactive structures to be produced under vacuum, but they need to be passivated to be incorporated into practical devices. Here, the facile protection of air-sensitive chiral graphene nanoribbons has been shown, by either hydrogenation or synthesis of an oxidized form. The chemically stable forms can subsequently be deprotected.

    • James Lawrence
    • , Alejandro Berdonces-Layunta
    •  & Dimas G. de Oteyza
  • Article |

    Supramolecular interactions play an essential role in organic electronic materials and biological systems. Now, it has been demonstrated that the σ–σ stacking interactions between neighbouring non-conjugated molecules can offer an efficient pathway for charge transport through supramolecular junctions, which provides a new guideline for the design and fabrication of organic materials and devices.

    • Anni Feng
    • , Yu Zhou
    •  & Wenjing Hong
  • Article |

    The strained topology of [n]paracyclophenylenes ([n]CPPs) typically prevents their π sysytem from being extended, but now the formation of a planar π-extended CPP has been achieved through a bottom-up on-surface synthesis approach. The planar π-extended [12]CPP produced by this method is a nanographene featuring an all-armchair edge, which leads to delocalized electronic states around the entire ring.

    • Feifei Xiang
    • , Sven Maisel
    •  & Sabine Maier
  • Review Article |

    The emerging field of dissipative DNA nanotechnology aims at developing synthetic devices and nanomaterials with life-like properties such as directional motion, transport, communication or adaptation. This Review surveys how dissipative DNA systems combine the programmability of nucleic-acid reactions with the consumption of energy stored in chemical fuel molecules to perform work and cyclical tasks.

    • Erica Del Grosso
    • , Elisa Franco
    •  & Francesco Ricci
  • Article |

    2D–2D heterostructures are typically held together by van der Waals interactions. Now, an on-device MoS2–graphene heterostructure has been prepared that is covalently linked through a bifunctional molecule featuring a maleimide and a diazonium group. The electronic properties of the resulting heterostructure are shown to be dominated by the molecular interface.

    • Manuel Vázquez Sulleiro
    • , Aysegul Develioglu
    •  & Emilio M. Pérez
  • Article |

    Information is physical, but the flow between information, energy and mechanics in chemical systems remains largely unexplored. Now, an autonomous molecular motor has been analysed with information thermodynamics, which relates information to other thermodynamic parameters. This treatment provides a general thermodynamic understanding of molecular motors, with practical implications for machine design.

    • Shuntaro Amano
    • , Massimiliano Esposito
    •  & Benjamin M. W. Roberts
  • Article |

    Controlling the crystallographic registry of layered materials through interlayer twist angles has introduced a distinctive degree of freedom for tuning their electronic behaviour. Now, the interfacial electrochemical kinetics of solution-phase redox complexes at twisted bilayer graphene electrodes have been modulated by the angle-dependent tuning of moiré-derived flat bands.

    • Yun Yu
    • , Kaidi Zhang
    •  & D. Kwabena Bediako
  • Article |

    Polyoxometalate clusters have been assembled into two-dimensional ‘clusterphene’ layers that are held together by coordination to lanthanide ions and electrostatic interactions with quaternary ammonium cations. The resulting materials resemble graphene sheets on account of their uniform hexagonal pores and are shown to catalyse epoxidation reactions due to their in-plane electron delocalization.

    • Qingda Liu
    • , Qinghua Zhang
    •  & Xun Wang
  • News & Views |

    Innovations in instrumentation together with new strategies of data collection and processing have been shown to solve the problem of data quality for time-resolved in situ X-ray diffraction studies on ball milling, opening new horizons in mechanochemistry.

    • Elena Boldyreva
  • News & Views |

    Bilayer borophene, predicted to be stabilized by interlayer linkages, has now been grown by molecular beam epitaxy on copper and silver surfaces in two independent studies. The growth substrate and temperature are found to influence the lattice structures formed.

    • Maryam Ebrahimi
  • Article |

    Electron spin resonance spectroscopy has traditionally been used to study large ensembles of spins, but its combination with scanning tunnelling microscopy recently enabled measurements on single adatoms. Now, individual iron phthalocyanine complexes adsorbed on a surface have been probed. Their spin distribution partially extends on the phthalocyanine, leading to a strong geometry-dependent exchange coupling interaction.

    • Xue Zhang
    • , Christoph Wolf
    •  & Taeyoung Choi
  • Article |

    Several polymorphs of borophene have been synthesized on metal substrates, but typically as monolayers. Now large-size, single-crystalline bilayer borophene has been grown on Cu(111)—a sufficient electron provider to enable the bonding of the second boron layer. The resulting bilayer possesses a metallic character and is less susceptible to oxidation than its monolayer counterpart.

    • Caiyun Chen
    • , Haifeng Lv
    •  & Lan Chen
  • Article |

    Layered materials held together by weak interactions can be exfoliated into monolayers that retain the structure and composition of their bulk counterpart, but this has remained challenging to achieve for non-van der Waals materials. Now, AgCrS2 has been exfoliated into such [CrS2]Ag[CrS2] nanosheets through intercalation with tetraalkylammonium cations chosen for their suitable redox potential. The nanosheets show superionic behaviour at room temperature.

    • Jing Peng
    • , Yuhua Liu
    •  & Yi Xie
  • Article |

    In biological systems, controlled molecular motion along a particular path is realized by protein motors that travel along microtubule filaments. Now, control of motion with light has been achieved in a synthetic supramolecular system, in which anionic porphyrin molecules move along the fibres of a bis-imidazolium gel upon irradiation.

    • Mario Samperi
    • , Bilel Bdiri
    •  & David B. Amabilino
  • Article |

    Spin-crossover nanoparticles have been covalently grafted onto a semiconducting MoS2 layer to form a self-strainable heterostructure. Under light or thermal stimulus, the nanoparticles switch between their high- and low-spin states, in which they have different volumes. This generates a reversible strain over the MoS2 layer and, in turn, alters the electrical and optical properties of the heterostructure.

    • Ramón Torres-Cavanillas
    • , Marc Morant-Giner
    •  & Eugenio Coronado
  • News & Views |

    Charged nanoparticles can behave as large ions or as small colloids. Their interaction with multivalent ions has now been shown to reflect this dichotomy, providing new paths to large, self-assembled nanoparticle superstructures.

    • Tobias Kraus
  • Article |

    Coulombic interactions can be used to assemble charged nanoparticles into higher-order structures, but this process typically requires similarly sized oppositely charged partners. Now, small anions or cations with as few as three charges have been shown to induce attractive interactions between oppositely charged nanoparticles in water, guiding the assembly of colloidal crystals.

    • Tong Bian
    • , Andrea Gardin
    •  & Rafal Klajn
  • News & Views |

    Among the tens of thousands of reported hybrid organic–inorganic crystals, only a small fraction of them are known to form a stable liquid upon heating. Now, a family of hybrid perovskites is shown to melt and, upon cooling, form glasses with a compelling combination of properties.

    • Morten M. Smedskjaer
    •  & Søren S. Sørensen
  • Article |

    Transition-metal single-atom catalysts display excellent activity per metal atom site, but suffer from low metal atom densities (typically less than 5 wt% or 1 at.%), which limits their overall catalytic performance. Now, the use of a graphene-quantum-dot primary support, later interweaved into a carbon matrix, has enabled the synthesis of single-atom catalysts with high transition-metal atom loadings of up to 40 wt% or 3.84 at.%.

    • Chuan Xia
    • , Yunrui Qiu
    •  & Haotian Wang
  • Article |

    On-surface, ultra-high vacuum conditions enable two-dimensional polymerizations to be precisely studied—often with submolecular resolution—but these syntheses are typically thermally activated, which can lead to high defect densities and relatively small domain sizes. Now, a self-assembled monolayer of a three-bladed fantrip monomer on alkane-passivated graphite has been covalently crosslinked into a mesoscale-ordered two-dimensional polymer by [4+4] photocycloaddition.

    • Lukas Grossmann
    • , Benjamin T. King
    •  & Markus Lackinger
  • News & Views |

    Colloidal self-assembly requires carefully balanced particle interactions that are often incompatible with the mechanical disturbances associated with macroscopic-scale manufacturing. Now, a practical bottom-up route has enabled the production of bulk solid materials with nanoscale components.

    • Theodore Hueckel
    •  & Stefano Sacanna
  • Article |

    Nanoparticulate platinum is a highly active catalyst, but it is scarce, expensive and not always sufficiently durable. Now, barium platinate has been used as a vehicle to preserve platinum as an oxide during the solid-state synthesis of a Pt-doped titanate perovskite; this enables the production of a structure with active and stable Pt nanoparticles on the perovskite surface that catalyses CO oxidation.

    • Maadhav Kothari
    • , Yukwon Jeon
    •  & John T. S. Irvine
  • Article |

    Open-shell nanographenes are promising for quantum technologies, but their magnetic stability has remained limited by weak exchange coupling. Now, two large rhombus-shaped nanographenes with zigzag peripheries, one with 48 carbon atoms and the other with 70, have been synthesized on gold and copper surfaces. The 70-carbon compound exhibits a large magnetic exchange coupling exceeding 100 meV.

    • Shantanu Mishra
    • , Xuelin Yao
    •  & Roman Fasel
  • Article |

    A series of dicyanamide-based hybrid organic–inorganic perovskite structures has been shown to melt at temperatures below 300 °C. On melt-quenching, they form glasses that possess coordination bonding and show very low thermal conductivities and moderate electrical conductivities as well as polymer-like thermomechanical properties.

    • Bikash Kumar Shaw
    • , Ashlea R. Hughes
    •  & Thomas D. Bennett
  • Article |

    A supramolecular three-shell matryoshka-like complex di rects the functionalization of the C60 inner shell to the selective formation of a single trans-3 fullerene bis-adduct. The selectivity with this matryoshka-like approach could be useful for applications where regioisomerically pure C60 bis-adducts have been shown to have superior properties compared with isomer mixtures.

    • Ernest Ubasart
    • , Oleg Borodin
    •  & Xavi Ribas