Inequivalent Solvation Effects on the N 1s Levels of Self-Associated Melamine Molecules in Aqueous Solution.

This work shows how the N 1s photoemission (PE) spectrum of self-associated melamine molecules in aqueous solution has been successfully rationalized using an integrated computational approach encompassing classical metadynamics simulations and quantum calculations based on density functional theory (DFT). The first approach allowed us to describe interacting melamine molecules in explicit waters and to identify dimeric configurations based on π-π and/or H-bonding interactions. Then, N 1s binding energies (BEs) and PE spectra were computed at the DFT level for all structures both in the gas phase and in an implicit solvent. While pure π-stacked dimers show gas-phase PE spectra almost identical to that of the monomer, those of the H-bonded dimers are sensibly affected by NH···NH or NH···NC interactions. Interestingly, the solvation suppresses all of the non-equivalences due to the H-bonds yielding similar PE spectra for all dimers, matching very well our measurements.

Probing Intermolecular H-Bonding Interactions in Cyanuric Acid Networks: Quenching of the N K-Edge Sigma Resonances.

The electronic characterization of the cyanuric acid both in gas phase and when embedded within an H-bonded scheme forming a monolayer on the Au(111) surface has been performed by means of X-ray Photoelectron Spectroscopy (XPS) and Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. The experimental spectra at the N, O, and C K-edges have been assigned with the support of DFT calculations, and the combination between theory and experiment has allowed to us investigate the effect of the H-bonding intermolecular interaction on the spectra. In particular, the H-bond formation in the monolayer leads to a quenching of the N 1s NEXAFS resonances associated with transitions to the sigma empty orbitals localized on the N-H portion of the imide group. On the other hand, the π* empty states remain substantially unperturbed. From a computational point of view, it has been shown that the DFT-TP scheme is not able to describe the N 1s NEXAFS spectra of these systems, and the configuration mixing has to be included, through the TDDFT approach in conjunction with the range-separated XC CAM-B3LYP functional, to obtain a correct reproduction of the N 1s core spectra.

Clarifying the Adsorption of Triphenylamine on Au(111): Filling the HOMO-LUMO Gap.

In this article, we analyze the electronic structure modifications of triphenylamine (TPA), a well-known electron donor molecule widely used in photovoltaics and optoelectronics, upon deposition on Au(111) at a monolayer coverage. A detailed study was carried out by synchrotron radiation-based photoelectron spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, scanning tunneling microscopy (STM), and ab initio calculations. We detect a new feature in the pre-edge energy region of the N K-edge NEXAFS spectrum that extends over 3 eV, which we assign to transitions involving new electronic states. According to our calculations, upon adsorption, a number of new unoccupied electronic states fill the energy region between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the free TPA molecule and give rise to the new feature in the pre-edge region of the NEXAFS spectrum. This finding highlights the occurrence of a considerable modification of the electronic structure of TPA. The appearance of new states in the HOMO-LUMO gap of TPA when adsorbed on Au(111) has crucial implications for the design of molecular nanoelectronic devices based on similar donor systems.

Tailoring surface-supported water-melamine complexes by cooperative H-bonding interactions.

The water-splitting photo-catalysis by carbon nitride heterocycles has been the subject of recent theoretical investigations, revealing a proton-coupled electron transfer (PCET) reaction from the H-bonded water molecule to the CN-heterocycle. In this context, a detailed characterization of the water-catalyst binding configuration becomes mandatory in order to validate and possibly improve the theoretical modeling. To this aim, we built a well-defined surface-supported water/catalyst interface by adsorbing water under ultra-high vacuum (UHV) conditions on a monolayer of melamine grown on the Cu(111) surface. By combining X-ray photoemission (XPS) and absorption (NEXAFS) spectroscopy we observed that melamine adsorbed onto copper is strongly tilted off the surface, with one amino group dangling to the vacuum side. The binding energy (BE) of the corresponding N 1s component is significantly higher compared to other N 1s contributions and displays a clear shift to lower BE as water is adsorbed. This finding along with density functional theory (DFT) results reveals that two adjacent melamine molecules concurrently work for stabilizing the H-bonded water-catalyst complex: one melamine acting as a H-donor via the amino-N (NH⋯OHH) and another one as a H-acceptor via the triazine-N (C[double bond, length as m-dash]N⋯HOH).

Surface effects on a photochromic spin-crossover iron(ii) molecular switch adsorbed on highly oriented pyrolytic graphite.

Thin films of an iron(ii) complex with a photochromic diarylethene-based ligand and featuring a spin-crossover behaviour have been grown by sublimation in ultra-high vacuum on highly oriented pyrolytic graphite and spectroscopically characterized through high-resolution X-ray and ultraviolet photoemission, as well as via X-ray absorption. Temperature-dependent studies demonstrated that the thermally induced spin-crossover is preserved at a sub-monolayer (0.7 ML) coverage. Although the photochromic ligand ad hoc integrated into the complex allows the photo-switching of the spin state of the complex at room temperature both in bulk and for a thick film on highly oriented pyrolytic graphite, this photomagnetic effect is not observed in sub-monolayer deposits. Ab initio calculations justify this behaviour as the result of specific adsorbate-substrate interactions leading to the stabilization of the photoinactive form of the diarylethene ligand over photoactive one on the surface.

Spectroscopic Fingerprints of Intermolecular H-Bonding Interactions in Carbon Nitride Model Compounds.

The effect of intermolecular H-bonding interactions on the local electronic structure of N-containing functional groups (amino group and pyridine-like N) that are characteristic of polymeric carbon nitride materials p-CN(H), a new class of metal-free organophotocatalysts, was investigated. Specifically, the melamine molecule, a building block of p-CN(H), was characterized by X-ray photoelectron (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. The molecule was studied as a noninteracting system in the gas phase and in the solid state within a H-bonded network. With the support of DFT simulations of the spectra, it was found that the H-bonds mainly affect the N 1s level of the amino group, leaving the N 1s level of the pyridine-like N mostly unperturbed. This is responsible for a reduction of the chemical shift between the two XPS N 1s levels relative to free melamine. Consequently, N K-edge NEXAFS resonances involving the amino N 1s level also shift to lower photon energies. Moreover, the solid-state absorption spectra showed significant modification/quenching of resonances related to transitions from the amino N 1s level to σ* orbitals involving the NH2 termini.

Partially Reversible Photoinduced Chemical Changes in a Mixed-Ion Perovskite Material for Solar Cells.

Metal halide perovskites have emerged as materials of high interest for solar energy-to-electricity conversion, and in particular, the use of mixed-ion structures has led to high power conversion efficiencies and improved stability. For this reason, it is important to develop means to obtain atomic level understanding of the photoinduced behavior of these materials including processes such as photoinduced phase separation and ion migration. In this paper, we implement a new methodology combining visible laser illumination of a mixed-ion perovskite ((FAPbI3)0.85(MAPbBr3)0.15) with the element specificity and chemical sensitivity of core-level photoelectron spectroscopy. By carrying out measurements at a synchrotron beamline optimized for low X-ray fluxes, we are able to avoid sample changes due to X-ray illumination and are therefore able to monitor what sample changes are induced by visible illumination only. We find that laser illumination causes partially reversible chemistry in the surface region, including enrichment of bromide at the surface, which could be related to a phase separation into bromide- and iodide-rich phases. We also observe a partially reversible formation of metallic lead in the perovskite structure. These processes occur on the time scale of minutes during illumination. The presented methodology has a large potential for understanding light-induced chemistry in photoactive materials and could specifically be extended to systematically study the impact of morphology and composition on the photostability of metal halide perovskites.

A Ru-Ru pair housed in ruthenium phthalocyanine: the role of a "cage" architecture in the molecule coupling with the Ag(111) surface.

A number of studies have investigated the properties of monomeric and double-decker phthalocyanines (Pcs) adsorbed on metal surfaces, in view of applications in spintronics devices. In a combined experimental and theoretical study, we consider here a different member of the Pcs family, the (RuPc)2 dimer, whose structure is characterized by two paired up magnetic centers embedded in a double-decker architecture. For (RuPc)2 on Ag(111), we show that this architecture works as a preserving cage by shielding the Ru-Ru pair from a direct interaction with the surface atoms. In fact, while noticeable surface-to-molecule charge transfer occurs with the ensuing quenching of the molecular magnetic moment, such phenomena occur here in the absence of a direct Ru-Ag coupling or structural rearrangement, at variance with other Pcs and thanks to the above shielding effect. These unique properties of the (RuPc)2 architecture are expected to permit an easy control of the surface-to-molecule charge-transfer process as well as of the molecular magnetic properties, thus making the (RuPc)2 dimer a significant paradigm for innovative "cage" structures as well as a promising candidate for applications in spintronics nano or single-molecule devices.

Magnetic fingerprint of individual Fe4 molecular magnets under compression by a scanning tunnelling microscope.

Single-molecule magnets (SMMs) present a promising avenue to develop spintronic technologies. Addressing individual molecules with electrical leads in SMM-based spintronic devices remains a ubiquitous challenge: interactions with metallic electrodes can drastically modify the SMM's properties by charge transfer or through changes in the molecular structure. Here, we probe electrical transport through individual Fe4 SMMs using a scanning tunnelling microscope at 0.5 K. Correlation of topographic and spectroscopic information permits identification of the spin excitation fingerprint of intact Fe4 molecules. Building from this, we find that the exchange coupling strength within the molecule's magnetic core is significantly enhanced. First-principles calculations support the conclusion that this is the result of confinement of the molecule in the two-contact junction formed by the microscope tip and the sample surface.

TiO2(110) Charge Donation to an Extended π-Conjugated Molecule.

The surface reduction of rutile TiO2(110) generates a state in the band gap whose excess electrons are spread among multiple sites, making the surface conductive and reactive. The charge extraction, hence the surface catalytic properties, depends critically on the spatial extent of the charge redistribution, which has been hitherto probed by small molecules that recombine at oxygen vacancy (Ovac) sites. We demonstrate by valence band resonant photoemission (RESPES) a very general charge extraction mechanism from a reduced TiO2(110) surface to an extended electron-acceptor organic molecule. Perylene-tetra-carboxylic-diimide (PTCDI) is not trapped at Ovac sites and forms a closely packed, planar layer on TiO2(110). In this configuration, the perylene core spills out the substrate excess electrons, filling the lowest unoccupied molecular orbital (LUMO). The charge transfer from the reduced surface to an extended π-conjugated system demonstrates the universality of the injection/extraction mechanism, opening new perspectives for the coupling of reducible oxides to organic semiconductors and supported catalysts.

Magnetic bistability in a submonolayer of sublimated Fe4 single-molecule magnets.

We demonstrate that Fe4 molecules can be deposited on gold by thermal sublimation in ultra-high vacuum with retention of single molecule magnet behavior. A magnetic hysteresis comparable to that found in bulk samples is indeed observed when a submonolayer film is studied by X-ray magnetic circular dichroism. Scanning tunneling microscopy evidences that Fe4 molecules are assembled in a two-dimensional lattice with short-range hexagonal order and coexist with a smaller contaminant. The presence of intact Fe4 molecules and the retention of their bistable magnetic behavior on the gold surface are supported by density functional theory calculations.

High resolution NEXAFS of perylene and PTCDI: a surface science approach to molecular orbital analysis.

We made use of synchrotron radiation to perform near edge X-ray absorption fine structure spectroscopy, NEXAFS, at the carbon K-edge of perylene and perylene-tetracarboxylic-diimide, PTCDI. Reference spectra measured for isolated molecules in the gas phase are compared with polarization dependent NEXAFS spectra measured on highly oriented thin films in order to study the symmetry of the molecular orbitals. The molecular overlayers are grown onto the rutile TiO2(110) surface for which the large anisotropic corrugation effectively drives the molecular orientation, while its dielectric nature prevents the rehybridization of the molecular orbitals. We employed density functional theory, DFT, calculations to disentangle the contribution of specific carbon atoms to the molecular density of states. Numerical simulations correctly predict the observed NEXAFS azimuthal dichroism of the σ* resonances above the ionization threshold, from which we determine the full geometric orientation of the overlayer molecules. A discrepancy observed for the spectral contribution of the imide carbon atom to the calculated unoccupied molecular orbitals has been explained in terms of initial state effects, as determined by Hartree-Fock corrections and in full agreement with the corresponding shift of the C 1s core level measured by X-ray photoelectron spectroscopy, XPS.

UHV deposition and characterization of a mononuclear iron(III) ß-diketonate complex on Au(111).

The adsorption of the sterically hindered ß-diketonate complex Fe(dpm)3, where Hdpm = dipivaloylmethane, on Au(111) was investigated by ultraviolet photoelectron spectroscopy (UPS) and scanning tunnelling microscopy (STM). The high volatility of the molecule limited the growth of the film to a few monolayers. While UPS evidenced the presence of the ß-diketonate ligands on the surface, the integrity of the molecule on the surface could not be assessed. The low temperature STM images were more informative and at submonolayer coverage they showed the presence of regular domains characterized by a flat morphology and height of ≈0.3 nm. Along with these domains, tetra-lobed features adsorbed on the kinks of the herringbone were also observed. DFT-simulated images of the pristine molecule and its possible decomposition products allowed to assess the partial fragmentation of Fe(dpm)3 upon adsorption on the Au(111) surface. Structural features with intact molecules were only observed for the saturation coverage. An ex situ prepared thick film of the complex was also investigated by X-ray magnetic circular dichroism (XMCD) and features typical of high-spin iron(III) in octahedral environment were observed.

Chemistry and temperature-assisted dehydrogenation of C60H30 molecules on TiO2(110) surfaces.

The thermal induced on-surface chemistry of large polycyclic aromatic hydrocarbons (PAHs) deposited on dielectric substrates is very rich and complex. We evidence temperature-assisted (cyclo)dehydrogenation reactions for C60H30 molecules and the subsequent bottom-up formation of assembled nanostructures, such as nanodomes, on the TiO2(110) surface. To this aim we have deposited, under ultra-high vacuum, a submonolayer coverage of C60H30 and studied, by a combination of experimental techniques (STM, XPS and NEXAFS) and theoretical methods, the different chemical on-surface interaction stages induced by the increasing temperature. We show that room temperature adsorbed molecules exhibit a weak interaction and freely diffuse on the surface, as previously reported for other aromatics. Nevertheless, a slight annealing induces a transition from this (meta)stable configuration into chemisorbed molecules. This adsorbate-surface interaction deforms the C60H30 molecular structure and quenches surface diffusion. Higher annealing temperatures lead to partial dehydrogenation, in which the molecule loses some of the hydrogen atoms and LUMO levels spread in the gap inducing a net total energy gain. Further annealing, up to around 750 K, leads to complete dehydrogenation. At these temperatures the fully dehydrogenated molecules link between them in a bottom-up coupling, forming nanodomes or fullerene-like monodisperse species readily on the dielectric surface. This work opens the door to the use of on-surface chemistry to generate new bottom-up tailored structures directly on high-K dielectric surfaces.

Weakly interacting molecular layer of spinning C60 molecules on TiO2 (110) surfaces.

The adsorption of C(60), a typical acceptor organic molecule, on a TiO(2) (110) surface has been investigated by a multitechnique combination, including van der Waals density functional calculations. It is shown that the adsorbed molecules form a weakly interacting molecular layer, which sits on the fivefold-coordinated Ti that is confined between the prominent bridging oxygen rows (see figure).

Preparation, reactivity and controlled release of SAMs of calix[4,6]arenes and calix[6]arene-based rotaxanes and pseudorotaxanes formed on polycrystalline Cu.

Specific and reversible binding of guest molecules from a solution to a surface pre-treated with host molecules is a recent and active field of research. Self-assembled monolayers may result from supramolecular interactions, adding distinct functionalities to the surface. In this frame, the first compared study is given here of the anchoring on the technologically relevant Cu surface of calix[4]arene receptors and calix[6]arene-based rotaxanes and pseudorotaxanes. These molecules, which belong to the most representative classes of compounds in supramolecular chemistry, have been chosen for their synthetic accessibility and versatility, which make them useful building blocks for the synthesis of new advanced supramolecular structures. Covalent functionalisation of calix[4,6]arenes on Cu was reached via a dip-coating procedure, optimizing the various synthetic aspects in order to obtain good coverages and copper passivation. Molecular adhesion has been demonstrated by the presence and relative quantitation of XPS signals from specific elements in the molecules. We have successfully tested the combination of different functionalities by producing a mixed film, prepared by ligand exchange of calix[4]arene with undecanethiol. The availability of the calix[4]arene cavity to reversibly host further species after anchoring on Cu has been demonstrated by a sequence of uptake and release cycles with pyridinium salts. Rotaxane and pseudorotaxane species, composed of a calix[6]arene wheel functionalized with N-phenylurea groups on the upper rim, and a viologen-containing axle, have been anchored on Cu via the SH-termination of the axle. XPS demonstrated the successful self-assembly of fully threaded rotaxanes and pseudorotaxanes from their solutions and the controlled release upon biasing of full rotaxanes and of the pseudorotaxane wheel.

Surface grafting and reactivity of calixarene-based receptors and pseudorotaxanes on Si(100).

The first report is given here on the anchoring on H-Si(100) of calix[4]arenes and calix[6]arene-based pseudorotaxanes, versatile building blocks for molecular devices. Covalent functionalization on Si was reached through a wet chemistry recipe, by making use of an extra-mild photochemical activation via visible light of C=C terminated anchoring arms. Our approach largely preserves the integrity of the molecular substrate, also allowing for a full monolayer of pseudorotaxane to be formed on Si(100). Molecular adhesion has been demonstrated by the presence and quantitation of XPS signals from specific elements in the molecules. AFM measurements performed on Si(100)/calix[4]arenes have revealed structures 2.3 nm high, consistent with the length of the molecule. The availability of the calix[4]arene cavity to host further species after anchoring on Si has been demonstrated by the successful complexation reaction with Cs(+) ions, resulting in a 1:1 calix/Cs(+) ratio, and with N-methyl pyridinium iodide. A pseudorotaxane species, composed of a calix[6]arene wheel derivatised with N-phenylureido groups on the upper rim and a viologen (4,4'-bipyridinium) containing axle, has been anchored on Si(100) via the C=C termination of the axle. We demonstrated the self-assembling of this pseudorotaxane covalently bound by use of XPS.

Selective assembling of calixarenes and pseudorotaxanes on Si(100) and polycrystalline copper.

We report the first compared study of the anchoring mode of calix[6]arene derivatives and pseudorotaxanes on Si(100) and polycrystalline Cu. Calixarenes have been chosen for their flexibility as linkers, being, i.a., efficient building blocks for the constructing of molecular devices based on pseudorotaxanes and rotaxanes. A covalent functionalization on Si or Cu surfaces requires the molecules to be differently modified: thiol (-SH) or C double bond C terminations are respectively suitable for Cu or H-Si(100). Anchoring on Cu was reached by dipping a clean substrate in a calix[6]arene-SH solution, while a wet-chemistry recipe was followed for Si(100), combined with an extra-mild photochemical activation via visible light. Molecular adhesion onto either surfaces has been demonstrated by the presence of XPS signals from specific elements in the molecules: calix[6]arene designed for H-Si were derivatized with NO2 groups on the upper rim of the calix, while the S atom was used as the molecular identifier on Cu. A further extension is represented by the anchoring reaction of rotaxanes on Si(100) and Cu surfaces. A pseudorotaxane species was first formed in solution by reacting a calix[6]arene "wheel," bearing three N-phenylureido groups on the upper rim, with viologen (4,4'-bipyridinium) containing axle. The resulting species has then been anchored on either Cu and Si via its distinct termination of the axle. This two-step reaction has produced a threaded pseudorotaxane covalently bound to either surfaces, as shown by XPS results. These species are ready to respond to external stimuli. We also cross-checked the two different anchoring groups for their reactivity on Cu and Si surfaces. No molecular uptake was observed when two solutions, containing calixarenes with the anchoring arms intended either for Si or Cu surfaces, were exchanged.