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The knowledge of the thermal expansion coefficient is of crucial importance to prevent the poor performance of devices, especially when these are made up of several layers of different materials, as in the case of 2D heterostructures. Helium atom scattering is a suitable tool for the direct measurement of the surface thermal expansion coefficient of materials. This information can be obtained directly from the position of the helium diffraction peaks, which allows determining the surface lattice constant at different temperatures by merely applying Bragg's law. We present new data for PdTe2 which confirm a trend observed for several 2D dichalcogenides, namely, that the in-plane lattice constant remains unchanged (within experimental error) in the temperature range of interest for applications, which enables setting an upper limit for the lateral thermal expansion coefficients of these materials. [ABSTRACT FROM AUTHOR]

Among the plethora of polycyclic structures that have emerged in recent years, indenofluorenes comprise a unique class of compounds due to their potential in organic electronic systems such as OLEDs, OFETs, and OPVCs. However, the synthesis of fully conjugated indenofluorenes without bulky groups on the apical carbons under standard chemistry conditions is not easily accessible. In this regard, on-surface synthesis has appeared as a newly developing field of research, which exploits the use of well-defined solid surfaces as confinement templates to initiate and develop chemical reactions. Here, we demonstrate the successful fabrication of indeno[1,2-b]fluorene π-conjugated polymers linked via cumulene-like connections on well-defined metallic surfaces under ultra-high vacuum conditions. The structure and electronic properties of the formed polymers have been precisely characterized by scanning tunneling microscopy, noncontact atomic force microscopy and scanning tunneling spectroscopy, complemented by computational investigations. [ABSTRACT FROM AUTHOR]

We have measured high-resolution time-of-flight (TOF) spectra of methane scattered from an Ir(111) surface at an incident energy of 81 meV. The angular distributions of scattered CH4 reveal the presence of a sharp and intense specular peak in addition to sharp features corresponding to rotationally inelastic diffraction (RID) peaks along the two main symmetry directions of Ir(111). TOF spectra have been recorded at several RID positions for the two high-symmetry directions. The data show that the scattering dynamics of CH4 is more complex than the one reported for H2/D2, where energy losses in TOF correspond to the expected excitation/deexcitation RID energy transitions. For CH4, this is the case only for RID peaks showing up far from the specular peak, whereas those appearing close to the specular position present different behaviors, depending on the incident direction. The results are compared with Ne scattering TOF data, which allows to assess the relevance of multiphonon scattering in the energy-exchange process. Finally, we report experimental evidence of selective adsorption resonances detected with CH4 beams. This will allow characterizing the CH4–metal surface physisorption well by measuring angular distributions with CH4 beams. [ABSTRACT FROM AUTHOR]

The interest in exploiting the unique properties of lanthanides has led to the recent design of two-dimensional coordination networks incorporating f-block elements on metallic surfaces. In order to take this field to the next step of progression, it is necessary to electronically decouple these two-dimensional architectures from the metallic surface underneath. As a first step in this direction, we report the formation of dysprosium-directed metal–organic networks employing three-fold ligands as molecular linkers equipped with terminal carbonitrile functional groups on weakly interacting substrates such as Au(111) and graphene/Ir(111). We observe on both substrates identical quasi-hexagonal Dy–carbonitrile coordination networks based on majority five-fold nodes. Our findings provide perspectives for the formation of lanthanide coordination networks on graphene and related sp2 materials grown on metals. [ABSTRACT FROM AUTHOR]

On-surface synthesis has recently become an essential approach toward the formation of carbon-based nanostructures. Special emphasis is set on the synthesis of π-conjugated polymers taking into consideration their relevance and potential in organic electronics, optoelectronics and spintronics. Here, we report the on-surface synthesis of conjugated ladder polymers consisting of pentacene units doubly-linked via ethynylene-like bonds on the Au(111) surface under ultra-high vacuum conditions. To this aim, we have sublimed pentacene-like precursors equipped with four :CBr2 functional groups to steer the desired reaction upon annealing on the surface. The atomically precise structure of the obtained polymers has been unambiguously characterized via low-temperature scanning tunneling microscopy and non-contact atomic force microscopy. In addition, scanning tunneling spectroscopy complemented with density-functional theory calculations reveal the narrow bandgap of the polymer. Our results provide potential for the synthesis of π-conjugated polymers with prospects in functional carbon-based nanomaterials that exploit multiple connections between molecular backbones. [ABSTRACT FROM AUTHOR]

One of the most attractive characteristics of some Prussian blue derivatives is the sensitivity of their magnetic properties to the irradiation with light. In this work photoinduced effects in the (Fe0.2Cr0.8)1.5[Cr(CN)6]·15H2O PBA have been studied by means of X-ray-based spectroscopies and magnetometry. It is found that the photosensitivity of this compound is mostly centred on the Fe cations: the exposure to green light induces a transfer of electrons from them to the Cr that provokes a reversal of the previously existing linkage isomerization and increases the elastic strain caused by the misfit of the unit cells of the Fe–NC–Cr and Cr–NC–Cr sublattices. The green light also quenches the magnetism of the FeII high-spin (HS) ions present in the sample and reduces the magnetic moments of most of the Cr cations except for CrII HS. Our study highlights the important role played by the mismatch between the unit cells of the coexisting sub-lattices in ternary Prussian blue analogues. [ABSTRACT FROM AUTHOR]

The appearance of magnetic order in the (Fe0.2Cr0.8)1.5[Cr(CN)6]·15H2O Prussian blue analogue at low temperature has been investigated by means of synchrotron radiation-based X-ray absorption spectroscopy and X-ray magnetic circular dichroism. With the help of ligand field multiplet analysis we have been able to identify the oxidation states of the metallic cations present in the sample and their evolution with temperature. Our experiments reveal that the appearance of ferromagnetic order is triggered by the transformation of CrIII cations to CrII high-spin caused by a transfer of electrons from the Fe to the Cr resulting in an increase of the magnetic interactions within the (Cr, Cr) sublattice. The misfit strain between the (Fe, Cr) and the (Cr, Cr) moieties that coexist within this ternary material influences the balance of oxidation states and hence the magnetic properties of the metallic ions. Misfit relaxation also plays a role in determining the differences between the surface and the bulk of the material. The measurement of the magnetic moments in those two regions suggests that the surface may have a reduced Curie temperature compared to the bulk. [ABSTRACT FROM AUTHOR]

We describe a method to functionalize graphene covalently with 92% yield and 98% site-selectivity and strict spatial periodicity on the nanometer scale. This method could be extended to other functional molecules. [ABSTRACT FROM AUTHOR]

The growth of a fullerene derivative (PCBM) on top of a layer of a tetrathiafulvalene (TTF) derivative previously deposited on Au(111) has been studied by scanning tunneling microscopy (STM). The results show that the preferential interaction with the gold substrate induces the exchange of PCBM molecules with the exTTF monolayer, expelling exTTF molecules to the outer surface. This exchange process is forbidden when the thickness of the exTTF layer increases above the monolayer, and the larger surface energy of PCBM leads to the growth of 3D islands. [ABSTRACT FROM AUTHOR]

We present a detailed experimental and theoretical study of elastic and rotationally inelastic diffraction of D2from NiAl(110) in the energy range 85–150 meV. The experiments were performed using a high-resolution, fixed angle geometry apparatus. Quantum and classical dynamical calculations were performed by using a six-dimensional potential energy surface constructed upon interpolation of a set of DFT (density functional theory) data. We show that, although elastic diffraction peak intensities are accurately described by theory in the whole range of incidence energies and angles explored, significant discrepancies are obtained for RID peaks, especially for those involving rotational initial states with ji> 0. Possible reasons for this discrepancy are discussed. [ABSTRACT FROM AUTHOR]

TCNQ derivatives adsorbed on a metal surface undergo a selflimited decyanation reaction that only affects two out of the four cyano groups in the molecule. Combined Scanning Tunneling Microscopy/X-ray Photoelectron Spectroscopy experiments and Density Functional Theory calculations relate the self-limiting behavior to the transfer of electrons from the metal to the molecule. [ABSTRACT FROM AUTHOR]

Ultra high vacuum scanning tunnelling microscopy revealed chlorosubphthalocyanine to self-organize into discrete well-defined bilayer and trilayer triangular nanocrystallites when evaporated onto a Cu(111) surface. [ABSTRACT FROM AUTHOR]

Graphene grown on Ir(111) electronically decouples adsorbed molecules from the metallic substrate and allows the study of their self-organization on surfaces. We study two electron acceptor molecules from the same family. The intermolecular interaction, attractive for TCNQ and repulsive for F4-TCNQ, dictates the molecular ordering. [ABSTRACT FROM AUTHOR]

The on-surface photogeneration of nonacene from α-bisdiketone precursors deposited on nanostructured epitaxial graphene grown on Ru(0001) has been studied by means of low temperature scanning tunneling microscopy and spectroscopy. The presence of an unoccupied surface state, spatially localized in the regions where the precursors are adsorbed, and energetically accessible in the region of the electromagnetic spectrum where n-π* transitions take place, allows for a 100% conversion of the precursors into nonacenes. With the help of state-of-the-art theoretical calculations, we show that such a high yield is due to the effective population of the surface state by the incoming light and the ensuing electron transfer to the unoccupied states of the precursors through an inelastic scattering mechanism. Our findings are the experimental confirmation that surface states can play a prominent role in the surface photochemistry of complex molecular systems, in accordance with early theoretical predictions made on small molecules.

We have measured high-resolution time-of-flight (TOF) spectra of methane scattered from an Ir(111) surface at an incident energy of 81 meV. The angular distributions of scattered CH 4 reveal the presence of a sharp and intense specular peak in addition to sharp features corresponding to rotationally inelastic diffraction (RID) peaks along the two main symmetry directions of Ir(111). TOF spectra have been recorded at several RID positions for the two high-symmetry directions. The data show that the scattering dynamics of CH 4 is more complex than the one reported for H 2 /D 2 , where energy losses in TOF correspond to the expected excitation/deexcitation RID energy transitions. For CH 4 , this is the case only for RID peaks showing up far from the specular peak, whereas those appearing close to the specular position present different behaviors, depending on the incident direction. The results are compared with Ne scattering TOF data, which allows to assess the relevance of multiphonon scattering in the energy-exchange process. Finally, we report experimental evidence of selective adsorption resonances detected with CH 4 beams. This will allow characterizing the CH 4 -metal surface physisorption well by measuring angular distributions with CH 4 beams.

The growth of a fullerene derivative (PCBM) on top of a layer of a tetrathiafulvalene (TTF) derivative previously deposited on Au(111) has been studied by scanning tunneling microscopy (STM). The results show that the preferential interaction with the gold substrate induces the exchange of PCBM molecules with the exTTF monolayer, expelling exTTF molecules to the outer surface. This exchange process is forbidden when the thickness of the exTTF layer increases above the monolayer, and the larger surface energy of PCBM leads to the growth of 3D islands.

Ultra high vacuum scanning tunnelling microscopy revealed chlorosubphthalocyanine to self-organize into discrete well-defined bilayer and trilayer triangular nanocrystallites when evaporated onto a Cu(111) surface.

We present a detailed experimental and theoretical study of elastic and rotationally inelastic diffraction of D(2) from NiAl(110) in the energy range 85-150 meV. The experiments were performed using a high-resolution, fixed angle geometry apparatus. Quantum and classical dynamical calculations were performed by using a six-dimensional potential energy surface constructed upon interpolation of a set of DFT (density functional theory) data. We show that, although elastic diffraction peak intensities are accurately described by theory in the whole range of incidence energies and angles explored, significant discrepancies are obtained for RID peaks, especially for those involving rotational initial states with j(i) > 0. Possible reasons for this discrepancy are discussed.