Structural characterization in on-surface synthesis is primarily carried out by Scanning Probe Microscopy (SPM) which provides high lateral resolution. Yet, important fresh perspectives on surface interactions and molecular conformations are gained from adsorption heights that remain largely inaccessible to SPM, but can be precisely measured with both elemental and chemical sensitivity by Normal-Incidence X-ray Standing Wave (NIXSW) analysis. Here, we study the evolution of adsorption heights in the on-surface synthesis and post-synthetic decoupling of porous covalent triazine–phenylene networks obtained from 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (TBPT) precursors on Ag(111). Room temperature deposition of TBPT and mild annealing to ∼150 °C result in full debromination and formation of organometallic intermediates, where the monomers are linked into reticulated networks by C–Ag–C bonds. Topologically identical covalent networks comprised of triazine vertices that are interconnected by biphenyl units are obtained by a thermally activated chemical transformation of the organometallic intermediates. Exposure to iodine vapor facilitates decoupling by intercalation of an iodine monolayer between the covalent networks and the Ag(111) surface. Accordingly, Scanning Tunneling Microscopy (STM), X-ray Photoelectron Spectroscopy (XPS) and NIXSW experiments are carried out for three successive sample stages: organometallic intermediates, covalent networks directly on Ag(111) and after decoupling. NIXSW analysis facilitates the determination of adsorption heights of chemically distinct carbon species, i.e. in the phenyl and triazine rings, and also for the organometallic carbon atoms. Thereby, molecular conformations are assessed for each sample stage. The interpretation of experimental results is informed by Density Functional Theory (DFT) calculations, providing a consistent picture of adsorption heights and molecular deformations in the networks that result from the interplay between steric hindrance and surface interactions. Quantitative adsorption heights, i.e. vertical distances between adsorbates and surface, provide detailed insight into surface interactions, but are underexplored in on-surface synthesis. In particular, the direct comparison with an in situ prepared decoupled state unveils the surface influence on the network structure, and shows that iodine intercalation is a powerful decoupling strategy.

Self‐assembly of three‐dimensional molecules is scarcely studied on surfaces. Their modes of adsorption can exhibit far greater variability compared to (nearly) planar molecules that adsorb mostly flat on surfaces. This additional degree of freedom can have decisive consequences for the expression of intermolecular binding motifs, hence the formation of supramolecular structures. The determining molecule‐surface interactions can be widely tuned, thereby providing a new powerful lever for crystal engineering in two dimensions. Here, we study the self‐assembly of triptycene derivatives with anthracene blades on Au(111) by Scanning Tunneling Microscopy, Near Edge X‐ray Absorption Fine Structure and Density Functional Theory. The impact of molecule‐surface interactions was experimentally tested by comparing pristine with iodine‐passivated Au(111) surfaces. Thereby, we observed a fundamental change of the adsorption mode that triggered self‐assembly of an entirely different structure.

The temporal evolution of the reactant concentrations as measured by XPS for different temperature profiles reveals that the debromination of organic molecules on Ag(111) is activated by Ag adatoms.

The dual-ion “Saltwater Battery” based on aqueous electrolyte containing sodium ions and lithium ions is believed to be one of the safest and environmentally friendliest battery technologies. The anode consists of sodium titanium phosphate, whereas the cathode is spinel lithium manganese oxide. It has been reported that both materials can intercalate sodium and lithium ions depending on their availability in the electrolyte. This study aims to identify the dominant active species in “Saltwater Batteries” with dual-ion electrolyte. Therefore, cyclic voltammetry of single electrodes as well as full cell measurements are performed with electrolyte containing lithium sulfate, sodium sulfate or a mixture. Moreover, the study is complemented by ion analysis of the electrolyte, as well as X-ray diffraction of fresh and cycled electrodes at different states of charge. The results show that the cathode only (de)intercalates lithium ions, revealing that Li is the dominant active cathode species. The anode can react with both ions and undergoes a formation reaction accompanied by partial dissolution of sodium titanium phosphate. Nevertheless, cyclic voltammetry and full cell measurements indicate that lithium is also the dominant active species on the anode side. In conclusion, the dual-ion battery is dominated by lithium and shows a superior performance when removing sodium from electrolyte.

A key milestone in the field of On‐Surface Synthesis (OSS) is the development of generic protocols for covalent coupling on inert surfaces. Typically, metal surfaces are used in OSS, but the strong interactions distort the intrinsic properties of the synthesized nanostructures and therefore compromise their applicability. Inert surfaces, on the other hand, preserve the nanostructures’ unique properties, but present challenges during synthesis: Activation energies are generally higher than on metal surfaces, hence thermally activated coupling on inert surfaces is severely hampered by competing premature desorption of the reactants. Using the coupling of 1,3,5‐tris(4‐mercaptophenyl)benzene (TMB) via carbon‐sulfur‐carbon thioether bonds, we demonstrate that annealing in a noble gas atmosphere instead of in a vacuum kinetically inhibits desorption. This allows covalent coupling on both inert graphite and even more weakly interacting graphene surfaces. We anticipate generic potential for this approach, with future experiments exploring the expandability of ambient pressure annealing to a portfolio of other coupling protocols.