Scanning probe microscopy articles within Nature Chemistry

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  • 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 |

    While aromaticity is a useful concept for assessing the reactivity of organic compounds, the connection between aromaticity and on-surface chemistry remains largely unexplored. Now, scanning probe experiments on cyclization reactions of porphyrins on Au(111) show that the peripheral carbon atoms outside of the aromatic 18-π electron pathway exhibit a higher reactivity.

    • Nan Cao
    • , Jonas Björk
    •  & Alexander Riss

  • Article |

    Monomeric N-heterocyclic carbenes (NHCs) can act as molecular modifiers of metal surfaces and thus affect heterogeneous catalytic behaviour. Now NHC polymers have been formed on gold surfaces, consisting of ballbot-type repeating units bound to single gold adatoms. Conformational, electronic and charge transport properties explain the high surface mobility of the incommensurate NHC polymers.

    • Jindong Ren
    • , Maximilian Koy
    •  & Frank Glorius

  • Review Article |

    The ability to detect and quantify a given analyte at the molecular level is a long-lasting goal for analytical and bioanalytical chemistry. This Review highlights how single-molecule junctions (SMJs) have been used for analytical purposes, from the detection of isomers and reaction intermediates to the detection of proteins and nucleic acids. Different SMJ approaches are discussed, along with their advantages and limitations over bulk analytical techniques.

    • Essam M. Dief
    • , Paul J. Low
    •  & Nadim Darwish

  • 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
    | 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 |

    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 |

    Meso–meso linked porphyrin arrays have been described as rod-like photonic wires. Now it has been shown that they can be bent into rings using template-directed synthesis. These rings of porphyrins mimic the light-harvesting arrays of chlorophyll molecules responsible for photosynthesis.

    • Henrik Gotfredsen
    • , Jie-Ren Deng
    •  & Harry L. Anderson

  • 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 |

    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

  • 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 |

    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

  • 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

  • News & Views |

    A series of mesoscale supramolecular hexagonal grids have been constructed in solution through stepwise intra- then intermolecular coordination-driven self-assembly, and characterized with atomic resolution by scanning tunnelling microscopy and spectroscopy.

    • Ruoning Li
    •  & Yongfeng Wang

  • Article |

    Some porous coordination polymers (PCPs) are known to be flexible and guest-responsive. Now, the guest-induced sharp, reversible structural transformation of the surface of a single-crystalline PCP has been visualized by in situ liquid-phase atomic force microscopy. This local response occurred at a guest concentration that was too low to trigger changes to the bulk crystal.

    • Nobuhiko Hosono
    • , Aya Terashima
    •  & Susumu Kitagawa

  • Article |

    MoS2 single layers spontaneously undergo a slow oxygen substitution reaction under ambient conditions giving rise to solid-solution-type 2D molybdenum oxy-sulfide crystals. The oxygen substitution sites of the 2D MoS2−xOx crystals act as efficient single-atom catalytic centres for the hydrogen evolution reaction.

    • János Pető
    • , Tamás Ollár
    •  & Levente Tapasztó

  • Article |

    On-surface polymerization is a promising technique to prepare organic functional nanomaterials, but it has remained difficult to carry out on insulating surfaces. Now, the photoinitiated radical polymerization of dimaleimide on KCl, initiated from a two-dimensional gas phase and guided by molecule–substrate interactions, has led to polymer fibres up to 1 μm long.

    • Franck Para
    • , Franck Bocquet
    •  & Matthew B. Watkins

  • Article |

    Atomic manipulation was used to control the reductive rearrangement of 1,1-dibromo alkenes to acetylenes on a NaCl surface at 5 K, and the stages of the reaction were visualized with atomic resolution using AFM. Polyynes ranging from triyne to octayne were prepared in this way, and STM was used to map their frontier orbitals and determine their transport gaps.

    • Niko Pavliček
    • , Przemyslaw Gawel
    •  & Leo Gross

  • Article |

    Complex interfacial supramolecular architectures promise unique physical and chemical properties, but are challenging to make. Now, it has been shown that a simple organic precursor can undergo a convergent multi-step on-surface transformation to give more complex building blocks that assemble into a semi-regular Archimedean tessellation with long-range order.

    • Yi-Qi Zhang
    • , Mateusz Paszkiewicz
    •  & Florian Klappenberger

  • Article |

    A renewed interest in C–H bond activation has developed on account of the recent increased availability of shale gas. Now, using a combination of surface science, microscopy, theory and nanoparticle studies, the ability of coke-resistant Pt/Cu single-atom alloys to efficiently activate C–H bonds in alkanes has been demonstrated under realistic catalytic conditions.

    • Matthew D. Marcinkowski
    • , Matthew T. Darby
    •  & E. Charles H. Sykes

  • News & Views |

    Using chiral modifiers on the surfaces of heterogeneous catalysts is a potentially fruitful route to practical stereoselective chemistry. Now, a study of the dynamics of prochiral adsorbates on modified surfaces has shown that they can rapidly interconvert between adsorption states of different prochirality.

    • Wilfred T. Tysoe

  • Article |

    A chiral molecule on a metal surface can set up a prochiral molecule for an enantioselective reaction step by forming a hydrogen-bonded complex that imposes a specific adsorption geometry. Time-lapsed scanning tunnelling microscopy and density functional theory studies reveal that such complexes can sometimes switch between states of opposing prochirality.

    • Guillaume Goubert
    • , Yi Dong
    •  & Peter H. McBreen

  • News & Views |

    Planar molecules may break mirror symmetry when aligned on a surface, but both right- and left-handed forms will be created. Starting with a single-handed precursor, chiral adsorbates of planar hydrocarbons with a single handedness are formed in on-surface reactions.

    • Karl-Heinz Ernst

  • Article |

    Flat, prochiral molecules form chiral adsorbates on achiral surfaces, but such assemblies are globally racemic. Now, it is shown that this mirror symmetry can be broken through stereocontrolled on-surface synthesis. Enantiopure helicene molecules can be transformed into flat, enantiofacially adsorbed products through a cascade of reactions on Ag(111) monitored by high-resolution scanning probe microscopy.

    • Oleksandr Stetsovych
    • , Martin Švec
    •  & Ivo Starý

  • Article |

    STM investigations and first principles calculations provide an understanding of the microscopic mechanism behind the mobility of N-heterocyclic carbenes (NHCs) on gold surfaces. Now, it is shown that a ballbot-type motion allows the formation of self-assembled monolayers due to the NHC extracting a gold atom from the surface, leading to a ligated gold adatom.

    • Gaoqiang Wang
    • , Andreas Rühling
    •  & Harald Fuchs

  • Article |

    Lateral anchoring of heteromolecules to graphene paves the way for the creation of hybrid materials with tunable properties. Now, following a surface-assisted dehydrogenative coupling reaction, the edges of graphene on silver have been functionalized with porphines. This enables the assembly of well-defined multifunctional graphene-based nanostructures.

    • Yuanqin He
    • , Manuela Garnica
    •  & Johannes V. Barth

  • Article |

    Force-induced tautomerization in a single porphycene molecule is investigated on a Cu(110) surface at 5 K by using non-contact atomic force microscopy. The force needed to trigger the tautomerization process is quantified by force spectroscopy and theoretical calculations reveal the atomistic mechanism behind the reaction.

    • Janina N. Ladenthin
    • , Thomas Frederiksen
    •  & Takashi Kumagai

  • Article |

    Quasicrystalline materials exhibit long-range order but no translational periodicity. Now, a random tiling quasicrystal has been fabricated on a Au(111) surface by coordination interactions between europium centres and linear dicarbonitrile linkers under stoichiometry control. The 2D metal–organic network exhibits the simultaneous presence of four-, five- and six-fold vertices and dodecagonal symmetry.

    • José I. Urgel
    • , David Écija
    •  & Johannes V. Barth

  • Article |

    The formation of homochiral supramolecular networks at solution–solid interfaces typically relies on the soldier-and-sergeant approach, in which a small amount of chiral modifier defines the handedness of the network. Now, judicious choice of the sergeant, solvent, temperature and concentration has enabled chiral induction pathways to be controlled so that a homochiral surface of either handedness can be assembled from the same system.

    • Yuan Fang
    • , Elke Ghijsens
    •  & Steven De Feyter

  • Article |

    The single-bond-resolved chemical structures of transient intermediates in a complex bimolecular reaction cascade were imaged by noncontact atomic force microscopy. Theoretical simulations reveal that the kinetic stabilization of experimentally observable intermediates is governed by selective energy dissipation to the substrate and entropic changes along the reaction pathway.

    • Alexander Riss
    • , Alejandro Pérez Paz
    •  & Felix R. Fischer

  • Article |

    Achiral minerals often adopt a chiral shape when crystal growth proceeds in contact with chiral molecules. Now, detailed microscopic insight is provided into how the chiral footprint of hemifullerene (a buckybowl that is essentially half of C60) rearranges atoms at step edges on a copper surface into chiral motifs.

    • Wende Xiao
    • , Karl-Heinz Ernst
    •  & Roman Fasel

  • Article |

    The Bergman cyclization is a fascinating rearrangement reaction with implications beyond organic chemistry. It has now been shown that a reversible Bergman cyclization reaction in a single molecule sitting on an ultrathin NaCl film can be triggered and directly imaged using atomic force microscopy. The interconverted diradical and diyne products are shown to have distinct chemical and physical properties.

    • Bruno Schuler
    • , Shadi Fatayer
    •  & Leo Gross

  • Article |

    Based initially on the outcome of certain reactions but later backed up by spectroscopic evidence, chemists have proposed — for more than a century — the existence of arynes as extremely reactive intermediates in chemical transformations. Now, with the help of atomic force microscopy, it is finally possible to generate and directly visualize this elusive intermediate.

    • Niko Pavliček
    • , Bruno Schuler
    •  & Leo Gross

  • News & Views |

    Defect-free Sierpiński triangles can be self-assembled on a silver surface through a combination of molecular design and thermal annealing. Three-fold halogen-bonding arrays and precise surface epitaxy preclude structural errors, thus enabling the high-level complexity of these supramolecular fractal patterns.

    • Steven L. Tait

  • Article |

    Biopolymers adopt functional tertiary structures through folding and multiplex formation. Synthetic molecules with protein-like dimensions — monodisperse cyclic porphyrin polymers with diameters of 13–21 nm — have now been shown to exhibit biomimetic self-organization by forming nested structures on a gold surface. These assemblies are formed both under vacuum and during deposition from solution.

    • Dmitry V. Kondratuk
    • , Luís M. A. Perdigão
    •  & Harry L. Anderson

  • News & Views |

    Quantitatively studying how the rate of a chemical reaction is affected by a reactant's atomic-scale environment is extremely challenging. This has now been achieved at the single-molecule level using scanning tunnelling microscopy to monitor tautomerization in an atomically well-defined environment.

    • Peter Liljeroth

  • Article |

    The rate of an intramolecular hydrogen transfer reaction in a single porphycene molecule resting on a copper surface can be controlled by placing a copper adatom close to it. Cooperativity effects are also observed in rows of porphycene molecules, where the reaction rate of each individual molecule depends on the precise tautomer state of its neighbours.

    • Takashi Kumagai
    • , Felix Hanke
    •  & Leonhard Grill

  • Article |

    A scanning tunnelling microscope has been used to image multistep chemical reactions at a solid/liquid interface with single-molecule resolution. On reacting Mn(III) porphyrins with either O2 or a single oxygen donor, at least four distinct reaction intermediates and products were detected and their interconversion could be observed in real space and real time.

    • Duncan den Boer
    • , Min Li
    •  & Johannes A. A. W. Elemans

  • News & Views |

    Characterizing electrochemical behaviour on the nanometre scale is fundamental to gaining complete insight into the working mechanisms of fuel cells. The application of a new scanning probe microscopy technique can now relate local surface structure to electrochemical activity at a resolution below 10 nm.

    • Johannes A. A. W. Elemans

  • Perspective |

    Recently, individual organic molecules have been imaged with atomic resolution using non-contact atomic force microscopy with functionalized tips and scanning tunnelling hydrogen microscopy. The resulting applications of these techniques and further improvements of ultra-high spatially resolved molecular investigations are discussed in this Perspective.

    • Leo Gross

  • News & Views |

    A series of scanning probe microscopy experiments combined with density functional theory calculations have now been used to unambiguously determine the structure of a marine natural product. Can this method become generally useful for the determination of the structure of natural products?

    • John W. Blunt

  • Research Highlights |

    The interactions between molecules on a surface have been directly imaged using scanning tunnelling microscopy.

    • Gavin Armstrong

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