Gas-Phase Transformation of Fluorinated Benzoporphyrins to Porphyrin-Embedded Conical Nanocarbons.

Geodesic nitrogen-containing graphene fragments are interesting candidates for various material applications, but the available synthetic protocols, which need to overcome intrinsic strain energy during the formation of the bowl-shaped skeletons, are often incompatible with heteroatom-embedded structures. Through this mass spectrometry-based gas-phase study, we show by means of collision-induced dissociation experiments and supported by density functional theory calculations, the first evidence for the formation of a porphyrin-embedded conical nanocarbon. The influences of metalation and functionalization of the used tetrabenzoporphyrins have been investigated, which revealed different cyclization efficiencies, different ionization possibilities, and a variation of the dissociation pathway. Our results suggest a stepwise process for HF elimination from the fjord region, which supports a selective pathway towards bent nitrogen-containing graphene fragments.

Phosphonic Acids on an Atomically Defined Oxide Surface: The Binding Motif Changes with Surface Coverage.

We have studied the anchoring mechanism of a phosphonic acid on an atomically defined oxide surface. Using time-resolved infrared reflection absorption spectroscopy, we investigated the reaction of deuterated phenylphosphonic acid (DPPA, C6H5PO3D2) with an atomically defined Co3O4(111) surface in situ during film growth by physical vapor deposition. We show that the binding motif of the phosphonate anchor group changes as a function of coverage. At low coverage, DPPA binds in the form of a chelating tridentate phosphonate, while a transition to a chelating bidentate occurs close to monolayer saturation coverage. However, the coverage-dependent change in the binding motif is not associated with a major change of the molecular orientation, suggesting that the rigid phosphonate linker always maintains the DPPA in a strongly tilted orientation irrespective of the surface coverage.

Model Catalytic Studies of Novel Liquid Organic Hydrogen Carriers: Indole, Indoline and Octahydroindole on Pt(111).

Indole derivatives were recently proposed as potential liquid organic hydrogen carriers (LOHC) for storage of renewable energies. In this work, we have investigated the adsorption, dehydrogenation and degradation mechanisms in the indole/indoline/octahydroindole system on Pt(111). We have combined infrared reflection absorption spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS) and DFT calculations. Indole multilayers show a crystallization transition at 200 K, in which the molecules adopt a strongly tilted orientation, before the multilayer desorbs at 220 K. For indoline, a less pronounced restructuring transition occurs at 150 K and multilayer desorption is observed at 200 K. Octahydroindole multilayers desorb already at 185 K, without any indication for restructuring. Adsorbed monolayers of all three compounds are stable up to room temperature and undergo deprotonation at the NH bond above 300 K. For indoline, the reaction is followed by partial dehydrogenation at the 5-membered ring, leading to the formation of a flat-lying di-σ-indolide in the temperature range from 330-390 K. Noteworthy, the same surface intermediate is formed from indole. In contrast, the reaction of octahydroindole with Pt(111) leads to the formation of a different intermediate, which originates from partial dehydrogenation of the 6-membered ring. Above 390 K, all three compounds again form the same strongly dehydrogenated and partially decomposed surface species.

Coverage-Dependent Anchoring of 4,4'-Biphenyl Dicarboxylic Acid to CoO(111) Thin Films.

We investigated the adsorption behavior of 4,4'-biphenhyl dicarboxylic acid (BDA) on well-ordered CoO(111) films grown on Ir(100) as a function of coverage and temperature using time-resolved and temperature-programmed infrared reflection absorption spectroscopy (TR-IRAS, TP-IRAS) in combination with density functional theory (DFT) and scanning tunneling microscopy (STM) under ultrahigh vacuum (UHV) conditions. To compare the binding behavior of BDA as a function of the oxide film thickness, three different CoO(111) film thicknesses were explored: films of about 20 bilayers (BLs) (approximately 5 nm), 2 BLs, and 1 BL. The two carboxylic acid groups of BDA offer two potential anchoring points to the oxide surface. At 150 K, intact BDA adsorbs on 20 BL thick oxide films in planar geometry with the phenyl rings aligned parallel to the surface. With decreasing oxide film thickness, we observe an increasing tendency for deprotonation and the formation of flat-lying BDA molecules anchored as dicarboxylates. After saturation of the first monolayer, intact BDA multilayers grow with molecules aligned parallel to the surface. The BDA multilayer desorbs at around 360 K. Completely different growth behavior is observed if BDA is deposited above the multilayer desorption temperature. Initially, doubly deprotonated dicarboxylates are formed by adopting a flat-lying orientation. With increasing exposure, however, the adsorbate layer transforms into upright standing monocarboxylates. A sharp OH stretching band (3584 cm-1) and a blue-shifted CO stretching band (1759 cm-1) indicate weakly interacting apical carboxylic acid groups at the vacuum interface. The anchored monocarboxylate phase slowly desorbs in a temperature range of up to 470 K. At higher temperature, a flat-lying doubly deprotonated BDA is formed, which desorbs and decomposes in a temperature range of up to 600 K.

Catalytically Triggered Energy Release from Strained Organic Molecules: The Surface Chemistry of Quadricyclane and Norbornadiene on Pt(111).

We have investigated the surface chemistry of the polycyclic valence-isomer pair norbornadiene (NBD) and quadricyclane (QC) on Pt(111). The NBD/QC system is considered to be a prototype for energy storage in strained organic compounds. By using a multimethod approach, including UV photoelectron, high-resolution X-ray photoelectron, and IR reflection-absorption spectroscopic analysis and DFT calculations, we could unambiguously identify and differentiate between the two molecules in the multilayer phase, which implies that the energy-loaded QC molecule is stable in this state. Upon adsorption in the (sub)monolayer regime, the different spectroscopies yielded identical spectra for NBD and QC at 125 and 160 K, when multilayer desorption takes place. This behavior is explained by a rapid cycloreversion of QC to NBD upon contact with the Pt surface. The NBD adsorbs in a η2 :η1 geometry with an agostic Pt-H interaction of the bridgehead CH2 subunit and the surface. Strong spectral changes are observed between 190 and 220 K because the hydrogen atom that forms the agostic bond is broke. This reaction yields a norbornadienyl intermediate species that is stable up to approximately 380 K. At higher temperatures, the molecule dehydrogenates and decomposes into smaller carbonaceous fragments.

Energy Storage in Strained Organic Molecules: (Spectro)Electrochemical Characterization of Norbornadiene and Quadricyclane.

We have investigated the electrochemically triggered cycloreversion of quadricyclane (QC) to norbornadiene (NBD), a system that holds the potential to combine both energy storage and conversion in a single molecule. Unambiguous voltammetric traces are obtained for pure NBD and pure QC, the latter a strained polycyclic isomer of the former. The difference in redox potentials is smaller than the energy difference between the neutral molecules. This is owing to a significant energy difference between the corresponding radical cations, as demonstrated by density functional theory (DFT) calculations. The vibrational modes of each pure compound are characterized experimentally in the fingerprint region and identified by DFT methods. Thermal and electrochemical transformations of NBD and QC are monitored in situ by IR spectroelectrochemical methods. The kinetics of the cycloreversion of QC to NBD, which is catalyzed by oxidizing equivalents, can be controlled by an applied electrode potential, which implies the ability to adjust in real time the release of thermal power stored in QC.

Functionalized Porphyrins on an Atomically Defined Oxide Surface: Anchoring and Coverage-Dependent Reorientation of MCTPP on Co3O4(111).

We have studied the adsorption of tetraphenylporphyrin (2HTPP) and its carboxylated counterpart mono-para-carboxyphenyltriphenylporphyrin (MCTPP) on an atomically defined Co3O4(111) film under ultrahigh vacuum (UHV) conditions. Using time-resolved infrared reflection absorption spectroscopy (TR-IRAS), we show that 2HTPP adsorbs molecularly in a flat-lying orientation, whereas MCTPP binds to the surface via formation of a chelating bidentate carboxylate upon deposition at 400 K. Combining TR-IRAS and density-functional theory (DFT), we determine the molecular tilting angle as a function of coverage. We show that the MCTPP adsorption geometry changes from a nearly flat-lying orientation (tilting angle <30°) at low coverage to a nearly perfectly upright-standing orientation (tilting angle of approximately 80°) in the full monolayer.

Molecular Orientation and Structural Transformations in Phthalic Anhydride Thin Films on MgO(100)/Ag(100).

Structural control of organic thin films on dielectric substrates is the key to tailoring the physical properties of hybrid materials, for example, for application in solar energy conversion, molecular electronics, or catalysis. In this work, we investigate the molecular orientation of phthalic anhydride (PAA) films on atomically well-defined MgO(100) on Ag(100) using temperature-programmed infrared reflection absorption spectroscopy (TP-IRAS) in combination with density-functional theory (DFT). A robust procedure is presented to determine the orientation of the PAA molecules, which relies on the intensity ratios of vibrational bands only. We show that even at deposition temperatures of 110 K, the PAA multilayer grows with a specific molecular orientation; that is, the PAA molecular plane is preferentially aligned parallel with the MgO surface. No change of molecular orientation occurs up to a temperature of 145 K. Between 145 and 160 K, the film restructures adopting a nearly flat-lying molecular orientation. Between 170 and 205 K, the film undergoes a second structural transition to a crystalline phase. This transition is associated with a pronounced molecular reorientation. The molecules adopt a tilted orientation and, simultaneously, rotate around their C2 axes. The reorientation behavior suggests that the molecular orientation in the crystalline phase is controlled by the interaction with the MgO(100) substrate. At higher temperature, no further restructuring is observed until the PAA multilayer desorbs at temperatures above 230 K.

Charge distribution analysis in Ag(n)(m⁺) clusters: molecular modeling and DFT calculations.

Neutral and charged silver clusters Ag63(m⁺) and Ag113(m⁺) (m=0,…,20) are investigated by simulated annealing molecular dynamics simulations. With increasing charge to size ratio the clusters undergo deformation to better accommodate surface charges. The latter are heterogeneously distributed and reflect the interplay of overall electrostatic repulsion and different degrees of local under-coordination of surface atoms. By comparison with atomic charges from natural population analysis based on density-functional calculations we demonstrate the suitability of the embedded-atom force-field in combination with the charge equilibrium approach.