Charge-Promoted Self-Metalation of Porphyrins on an Oxide Surface.

Metalation and self-metalation reactions of porphyrins on oxide surfaces have recently gained interest. The mechanism of porphyrin self-metalation on oxides is, however, far from being understood. Herein, we show by a combination of results obtained with scanning tunneling microscopy, photoemission spectroscopy, and DFT computations, that the self-metalation of 2H-tetraphenylporphyrin on the surface of ultrathin MgO(001) films is promoted by charge transfer. By tuning the work function of the MgO(001)/Ag(001) substrate, we are able to control the charge and the metalation state of the porphyrin molecules on the surface.

Momentum space imaging of σ orbitals for chemical analysis.

Tracing the modifications of molecules in surface chemical reactions benefits from the possibility to image their orbitals. While delocalized frontier orbitals with π character are imaged routinely with photoemission orbital tomography, they are not always sensitive to local chemical modifications, particularly the making and breaking of bonds at the molecular periphery. For such bonds, σ orbitals would be far more revealing. Here, we show that these orbitals can indeed be imaged in a remarkably broad energy range and that the plane wave approximation, an important ingredient of photoemission orbital tomography, is also well fulfilled for these orbitals. This makes photoemission orbital tomography a unique tool for the detailed analysis of surface chemical reactions. We demonstrate this by identifying the reaction product of a dehalogenation and cyclodehydrogenation reaction.

Hexacene on Cu(110) and Ag(110): Influence of the Substrate on Molecular Orientation and Interfacial Charge Transfer.

Hexacene, composed of six linearly fused benzene rings, is an organic semiconductor material with superior electronic properties. The fundamental understanding of the electronic and chemical properties is prerequisite to any possible application in devices. We investigate the orientation and interface properties of highly ordered hexacene monolayers on Ag(110) and Cu(110) with X-ray photoemission spectroscopy (XPS), photoemission orbital tomography (POT), X-ray absorption spectroscopy (XAS), low-energy electron diffraction (LEED), scanning tunneling microscopy (STM), and density functional theory (DFT). We find pronounced differences in the structural arrangement of the molecules and the electronic properties at the metal/organic interfaces for the two substrates. While on Cu(110) the molecules adsorb with their long molecular axis parallel to the high symmetry substrate direction, on Ag(110), hexacene adsorbs in an azimuthally slightly rotated geometry with respect to the metal rows of the substrate. In both cases, molecular planes are oriented parallel to the substrate. A pronounced charge transfer from both substrates to different molecular states affects the effective charge of different C atoms of the molecule. Through analysis of experimental and theoretical data, we found out that on Ag(110) the LUMO of the molecule is occupied through charge transfer from the metal, whereas on Cu(110) even the LUMO+1 receives a charge. Interface dipoles are determined to a large extent by the push-back effect, which are also found to differ significantly between 6A/Ag(110) and 6A/Cu(110).

Large Distortion of Fused Aromatics on Dielectric Interlayers Quantified by Photoemission Orbital Tomography.

Polycyclic aromatic compounds with fused benzene rings offer an extraordinary versatility as next-generation organic semiconducting materials for nanoelectronics and optoelectronics due to their tunable characteristics, including charge-carrier mobility and optical absorption. Nonplanarity can be an additional parameter to customize their electronic and optical properties without changing the aromatic core. In this work, we report a combined experimental and theoretical study in which we directly observe large, geometry-induced modifications in the frontier orbitals of a prototypical dye molecule when adsorbed on an atomically thin dielectric interlayer on a metallic substrate. Experimentally, we employ angle-resolved photoemission experiments, interpreted in the framework of the photoemission orbital tomography technique. We demonstrate its sensitivity to detect geometrical bends in adsorbed molecules and highlight the role of the photon energy used in experiment for detecting such geometrical distortions. Theoretically, we conduct density functional calculations to determine the geometric and electronic structure of the adsorbed molecule and simulate the photoemission angular distribution patterns. While we found an overall good agreement between experimental and theoretical data, our results also unveil limitations in current van der Waals corrected density functional approaches for such organic/dielectric interfaces. Hence, photoemission orbital tomography provides a vital experimental benchmark for such systems. By comparison with the state of the same molecule on a metallic substrate, we also offer an explanation why the adsorption on the dielectric induces such large bends in the molecule.

Going beyond Pentacene: Photoemission Tomography of a Heptacene Monolayer on Ag(110).

Longer acenes such as heptacene are promising candidates for optoelectronic applications but are unstable in their bulk structure as they tend to dimerize. This makes the growth of well-defined monolayers and films problematic. In this article, we report the successful preparation of a highly oriented monolayer of heptacene on Ag(110) by thermal cycloreversion of diheptacenes. In a combined effort of angle-resolved photoemission spectroscopy and density functional theory (DFT) calculations, we characterize the electronic and structural properties of the molecule on the surface in detail. Our investigations allow us to unambiguously confirm the successful fabrication of a highly oriented complete monolayer of heptacene and to describe its electronic structure. By comparing experimental momentum maps of photoemission from frontier orbitals of heptacene and pentacene, we shed light on differences between these two acenes regarding their molecular orientation and energy-level alignment on the metal surfaces.

Controlling the electronic and physical coupling on dielectric thin films.

Ultrathin dielectric/insulating films on metals are often used as decoupling layers to allow for the study of the electronic properties of adsorbed molecules without electronic interference from the underlying metal substrate. However, the presence of such decoupling layers may effectively change the electron donating properties of the substrate, for example, by lowering its work function and thus enhancing the charging of the molecular adsorbate layer through electron tunneling. Here, an experimental study of the charging of para-sexiphenyl (6P) on ultrathin MgO(100) films supported on Ag(100) is reported. By deliberately changing the work function of the MgO(100)/Ag(100) system, it is shown that the charge transfer (electronic coupling) into the 6P molecules can be controlled, and 6P monolayers with uncharged molecules (Schottky-Mott regime) and charged and uncharged molecules (Fermi level pinning regime) can be obtained. Furthermore, it was found that charge transfer and temperature strongly influence the orientation, conformation, and wetting behavior (physical coupling) of the 6P layers on the MgO(100) thin films.

Kekulene: On-Surface Synthesis, Orbital Structure, and Aromatic Stabilization.

We revisit the question of kekulene's aromaticity by focusing on the electronic structure of its frontier orbitals as determined by angle-resolved photoemission spectroscopy. To this end, we have developed a specially designed precursor, 1,4,7(2,7)-triphenanthrenacyclononaphane-2,5,8-triene, which allows us to prepare sufficient quantities of kekulene of high purity directly on a Cu(111) surface, as confirmed by scanning tunneling microscopy. Supported by density functional calculations, we determine the orbital structure of kekulene's highest occupied molecular orbital by photoemission tomography. In agreement with a recent aromaticity assessment of kekulene based solely on C-C bond lengths, we conclude that the π-conjugation of kekulene is better described by the Clar model rather than a superaromatic model. Thus, by exploiting the capabilities of photoemission tomography, we shed light on the question which consequences aromaticity holds for the frontier electronic structure of a π-conjugated molecule.