Quantum Tunneling Mediated Interfacial Synthesis of a Benzofuran Derivative.

Reaction pathways involving quantum tunneling of protons are fundamental to chemistry and biology. They are responsible for essential aspects of interstellar synthesis, the degradation and isomerization of compounds, enzymatic activity, and protein dynamics. On-surface conditions have been demonstrated to open alternative routes for organic synthesis, often with intricate transformations not accessible in solution. Here, we investigate a hydroalkoxylation reaction of a molecular species adsorbed on a Ag(111) surface by scanning tunneling microscopy complemented by X-ray electron spectroscopy and density functional theory. The closure of the furan ring proceeds at low temperature (down to 150 K) and without detectable side reactions. We unravel a proton-tunneling-mediated pathway theoretically and confirm experimentally its dominant contribution through the kinetic isotope effect with the deuterated derivative.

On-Surface Activation of Trimethylsilyl-Terminated Alkynes on Coinage Metal Surfaces.

The controlled attachment of protecting groups combined with the ability to selectively abstract them is central to organic synthesis. The trimethylsilyl (TMS) functional group is a popular protecting group in solution. However, insights on its activation behavior under ultra-high vacuum (UHV) and surface-confined conditions are scarce. Here we investigate a series of TMS-protected alkyne precursors via scanning tunneling microscopy (STM) regarding their compatibility with organic molecular beam epitaxy (OMBE) and their potential deprotection on various coinage metal surfaces. After in-situ evaporation on the substrates held in UHV at room temperature, we find that all molecules arrived and adsorbed as intact units forming ordered supramolecular aggregates stabilized by non-covalent interactions. Thus, TMS-functionalized alkyne precursors with weights up to 1100 atomic mass units are stable against OMBE evaporation in UHV. Furthermore, the TMS activation through thermal annealing is investigated with STM and X-ray photoelectron spectroscopy (XPS). We observe that deprotection starts to occur between 400 K and 500 K on the copper and gold surfaces, respectively. In contrast, on silver surfaces, the TMS-alkyne bond remains stable up to temperatures where molecular desorption sets in (≈600 K). Hence, TMS functional groups can be utilized as leaving groups on copper and gold surfaces while they serve as protecting groups on silver surfaces.

Surface-Dependent Chemoselectivity in C-C Coupling Reactions.

Surface-confined covalent coupling reactions of the linear compound 4-(but-3-en-1-ynyl)-4'-ethynyl-1,1'-biphenyl (1), which contains one alkyne and one enyne group on opposing ends, have been investigated using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. The reactions show a surface-dependent chemoselectivity: on Au(111), compound 1 preferentially yields cyclotrimerization products, while on Cu(111), a selective coupling between the enyne and alkyne groups is observed. Linear, V-shaped string formations combined with Y-shaped bifurcation motifs result in a random reticulation on the entire surface. DFT calculations show that the C-H⋅⋅⋅πδ- transition state of the reaction between the deprotonated alkyne group and a nearby H-donor of the alkene group plays a key role in the mechanism and high chemoselectivity. This study highlights a concept that opens new avenues to the surface-confined synthesis of covalent carbon-based sp-sp2 polymers.

Synthesizing Highly Regular Single-Layer Alkynyl-Silver Networks at the Micrometer Scale via Gas-Mediated Surface Reaction.

Extended organometallic honeycomb alkynyl-silver networks have been synthesized on a noble metal surface under ultrahigh vacuum conditions via a gas-mediated surface reaction protocol. Specifically, the controlled exposure to molecular oxygen efficiently deprotonates terminal alkyne moieties of 1,3,5-tris(4-ethynylphenyl)benzene (Ext-TEB) precursors adsorbed on Ag(111). At Tsub = 200 K, this O2-mediated reaction pathway features high chemoselectivity without poisoning the surface. Through mild annealing to 375 K, long-range ordered alkynyl-silver networks incorporating substrate atoms evolve, featuring Ag- bis-acetylide motifs, high structural quality and a regular arrangement of nanopores with a van der Waals cavity of ≈8.3 nm2.

Assembly of Robust Holmium-Directed 2D Metal-Organic Coordination Complexes and Networks on the Ag(100) Surface.

We describe the formation of lanthanide-organic coordination networks and complexes under ultra-high-vacuum conditions on a clean Ag(100) surface. The structures comprise single Ho atoms as coordination centers and 1,4-benzenedicarboxylate (from terephtalic acid, TPA) as molecular linkers. Using low-temperature scanning tunneling microscopy, we find two different chiral phases of surface-supported metal-organic structures incorporating Ho atoms. Density functional theory calculations can explain the structure of both binding motifs and give possible reasons for their varying formation under the respective Ho/TPA ratios, as well as deposition and annealing temperatures. Metal-ligand interactions drive the formation of cloverleaf-shaped mononuclear Ho-TPA4 complexes establishing supramolecular arrays stabilized through hydrogen bonding. A 2D lanthanide-organic reticulation is observed when changing the stoichiometry between the two building blocks. The combined insights from scanning tunneling microscopy and density functional theory reveal the relative stability, charge transfer, and bonding environment of both motifs.

Isomerism control of diethylstilbestrol by metal surface induced O-H cleavage.

Diethylstilbestrol (DES) is studied on Ag(111) and Cu(111) surfaces using X-ray photoelectron spectroscopy (XPS) and scanning tunnelling microscopy (STM). We find that DES molecules on the silver surface adsorb intact and adopt a trans-conformation. On the more reactive copper surface, O-H bond cleavage results in molecular adsorption in the cis-conformation, thus providing the means of obtaining different adsorption geometries. The difference in isomerism is reflected in the observed self-assemblies which exhibit room-temperature stability.

Unraveling the Oxidation and Spin State of Mn-Corrole through X-ray Spectroscopy and Quantum Chemical Analysis.

The interplay between Mn ions and corrole ligands gives rise to complex scenarios regarding the metal centers' electronic properties expressing a range of high oxidation states and spin configurations. The resulting potential of Mn-corroles for applications such as catalysts or fuel cells has recently been demonstrated. However, despite being crucial for their functionality, the electronic structure of Mn-corroles is often hardly accessible with traditional techniques and thus is still under debate, especially under interfacial conditions. Here, we unravel the electronic ground state of the prototypical Mn-5,10,15-tris(pentafluorophenyl)corrole complex through X-ray spectroscopic investigations of ultrapure thin films and quantum chemical analysis. The theory-based interpretation of Mn photoemission and absorption fine structure spectra (3s and 2p and L2,3-edge, respectively) evidence a Mn(III) oxidation state with an S = 2 high-spin configuration. By referencing density functional theory calculations with the experiments, we lay the basis for extending our approach to the characterization of complex interfaces.

Ho-Mediated Alkyne Reactions at Low Temperatures on Ag(111).

Low-temperature approaches to catalytic conversions promise efficiency, selectivity, and sustainable processes. Control over certain coupling reactions can be obtained via the pre-positioning of reactive moieties by self-assembly. However, in the striving field of on-surface synthesis atomistic precision and control remains largely elusive, because the employed coupling reactions proceed at temperatures beyond the thermal stability of the supramolecular templates. Here, utilizing scanning tunneling microscopy, we demonstrate terminal alkyne on-surface reactions mediated by Ho atoms at a weakly reactive Ag(111) substrate at low-temperatures. Density functional theory calculations confirm the catalytic activity of the involved adatoms. Pre-deposited Ho induces alkyne dehydrogenation starting at substrate temperatures as low as 100 K. Ho arriving at molecularly pre-covered surfaces held at 130 and 200 K produces covalent enyne-linked dimers and initiates cyclotrimerization, respectively. Statistical product analysis indicates a two-step pathway for the latter, whereby the enyne intermediates influence the distribution of the products. High chemoselectivity results from the absence of cyclotetramerization and diyne-forming homocoupling. Our analysis indicates that mainly the arriving Ho adatoms enable the coupling. These findings support the concept of dynamic heterogeneity by single-atom catalysts and pave the way for alternative means to control on-surface reactions.

Complex supramolecular interfacial tessellation through convergent multi-step reaction of a dissymmetric simple organic precursor.

Interfacial supramolecular self-assembly represents a powerful tool for constructing regular and quasicrystalline materials. In particular, complex two-dimensional molecular tessellations, such as semi-regular Archimedean tilings with regular polygons, promise unique properties related to their nontrivial structures. However, their formation is challenging, because current methods are largely limited to the direct assembly of precursors, that is, where structure formation relies on molecular interactions without using chemical transformations. Here, we have chosen ethynyl-iodophenanthrene (which features dissymmetry in both geometry and reactivity) as a single starting precursor to generate the rare semi-regular (3.4.6.4) Archimedean tiling with long-range order on an atomically flat substrate through a multi-step reaction. Intriguingly, the individual chemical transformations converge to form a symmetric alkynyl-Ag-alkynyl complex as the new tecton in high yields. Using a combination of microscopy and X-ray spectroscopy tools, as well as computational modelling, we show that in situ generated catalytic Ag complexes mediate the tecton conversion.

Functionalized Graphdiyne Nanowires: On-Surface Synthesis and Assessment of Band Structure, Flexibility, and Information Storage Potential.

Carbon nanomaterials exhibit extraordinary mechanical and electronic properties desirable for future technologies. Beyond the popular sp2 -scaffolds, there is growing interest in their graphdiyne-related counterparts incorporating both sp2 and sp bonding in a regular scheme. Herein, we introduce carbonitrile-functionalized graphdiyne nanowires, as a novel conjugated, one-dimensional (1D) carbon nanomaterial systematically combining the virtues of covalent coupling and supramolecular concepts that are fabricated by on-surface synthesis. Specifically, a terphenylene backbone is extended with reactive terminal alkyne and polar carbonitrile (CN) moieties providing the required functionalities. It is demonstrated that the CN functionalization enables highly selective alkyne homocoupling forming polymer strands and gives rise to mutual lateral attraction entailing room-temperature stable double-stranded assemblies. By exploiting the templating effect of the vicinal Ag(455) surface, 40 nm long semiconducting nanowires are obtained and the first experimental assessment of their electronic band structure is achieved by angle-resolved photoemission spectroscopy indicating an effective mass below 0.1m0 for the top of the highest occupied band. Via molecular manipulation it is showcased that the novel oligomer exhibits extreme mechanical flexibility and opens unexplored ways of information encoding in clearly distinguishable CN-phenyl trans-cis species. Thus, conformational data storage with density of 0.36 bit nm-2 and temperature stability beyond 150 K comes in reach.

Terminal Alkyne Coupling on a Corrugated Noble Metal Surface: From Controlled Precursor Alignment to Selective Reactions.

Surface-templated covalent coupling of organic precursors currently emerges as a promising route to the atom-precise fabrication of low-dimensional carbon materials. Here, we investigate the adsorption and the coupling reactions of 4,4''-diethynyl-1,1':4',1''-terphenyl on Au(110) under ultra-high vacuum conditions by using scanning tunneling microscopy combined with density functional theory and kinetic Monte Carlo calculations. Temperature treatment induces both 1,2,4-asymmetric cyclotrimerization and homocoupling, resulting in various reaction products, including a previously unreported, surface-templated H-shaped pentamer. Our analysis of the temperature-dependent relative product abundances unravels that 1,2,4-trimerization and homocoupling proceed via identical intermediate species with the final products depending on the competition of coupling to a third monomer versus dehydrogenation. Our study sheds light on the control of coupling reactions by corrugated surfaces and annealing protocols.

One-Dimensionally Disordered Chiral Sorting by Racemic Tiling in a Surface-Confined Supramolecular Assembly of Achiral Tectons.

The aggregation of (pro)chiral/achiral molecules into crystalline structures at interfaces forms conglomerates, racemates, and solid solutions, comparable to known bulk phases. Scanning tunneling microscopy and Monte Carlo simulations were employed to uncover a distinct racemic phase, expressing 1D disordered chiral sorting through random tiling in surface-confined supramolecularly assembled achiral 4,4''-diethynyl-1,1':4',1''-terphenyl molecules. The configurational entropy of the 1D disordered racemic tiling phase was verified by analytical modeling, and found to lie between that of a perfectly ordered 2D racemate and a racemic solid solution.

On-Surface Site-Selective Cyclization of Corrole Radicals.

Radical cyclization is among the most powerful and versatile reactions for constructing mono- and polycyclic systems, but has, to date, remained unexplored in the context of on-surface synthesis. We report the controlled on-surface synthesis of stable corrole radicals on Ag(111) via site-specific dehydrogenation of a pyrrole N-H bond in the 5,10,15-tris(pentafluoro-phenyl)-corrole triggered by annealing at 330 K under ultrahigh-vacuum conditions. We reveal a thermally induced regioselective cyclization reaction mediated by a radical cascade and resolve the reaction mechanism of the pertaining cyclodefluorination reaction at the single-molecule level. Via intramolecularly resolved probing of the radical-related Kondo signature, we achieve real space visualization of the distribution of the unpaired electron density over specific sites within the corrole radical. Annealing to 550 K initiates intermolecular coupling reactions, producing an extended π-conjugated corrole system.

Epitaxy-Induced Assembly and Enantiomeric Switching of an On-Surface Formed Dinuclear Organocobalt Complex.

We report on the surface-guided synthesis of a dinuclear organocobalt complex, its self-assembly into a complex nanoarchitecture, and a single-molecule level investigation of its switching behavior. Initially, an organic layer is prepared by depositing hexakis((trimethylsilyl)ethynyl)-benzene under ultrahigh-vacuum conditions onto Ag(111). After Co dosage at 200 K, low-temperature scanning tunneling microscopy (STM) reveals an epitaxy-mediated organization mechanism of molecules and on-surface formed organometallic complexes. The dinuclear complexes contain two bis(η2-alkynyl) π-tweezer motifs, each stabilizing a single Co atom and express two enantiomers due to a conformation twist. The chirality is transferred to the two-dimensional architecture, whereby its Co adatoms are located at the corners of a 3.4.6.4 rhombitrihexagonal tessellation due to the systematic arrangement and anchoring of the complexes. Extensive density functional theory simulations support our interpretation of an epitaxy-guided surface tessellation and its chiral character. Additionally, STM tip-assisted manipulation experiments on isolated dinuclear complexes reveal controlled and reversible switching between the enantiomeric states via inelastic electron processes. After activation by bias pulses, structurally modified complexes display a distinctive Kondo feature attributed to metastable Co configurations.

Synthesis of Graphene Nanoribbons by Ambient-Pressure Chemical Vapor Deposition and Device Integration.

Graphene nanoribbons (GNRs), quasi-one-dimensional graphene strips, have shown great potential for nanoscale electronics, optoelectronics, and photonics. Atomically precise GNRs can be "bottom-up" synthesized by surface-assisted assembly of molecular building blocks under ultra-high-vacuum conditions. However, large-scale and efficient synthesis of such GNRs at low cost remains a significant challenge. Here we report an efficient "bottom-up" chemical vapor deposition (CVD) process for inexpensive and high-throughput growth of structurally defined GNRs with varying structures under ambient-pressure conditions. The high quality of our CVD-grown GNRs is validated by a combination of different spectroscopic and microscopic characterizations. Facile, large-area transfer of GNRs onto insulating substrates and subsequent device fabrication demonstrate their promising potential as semiconducting materials, exhibiting high current on/off ratios up to 6000 in field-effect transistor devices. This value is 3 orders of magnitude higher than values reported so far for other thin-film transistors of structurally defined GNRs. Notably, on-surface mass spectrometry analyses of polymer precursors provide unprecedented evidence for the chemical structures of the resulting GNRs, especially the heteroatom doping and heterojunctions. These results pave the way toward the scalable and controllable growth of GNRs for future applications.

Supramolecular Spangling, Crocheting, and Knitting of Functionalized Pyrene Molecules on a Silver Surface.

Pyrenes, as photoactive polycyclic aromatic hydrocarbons (PAHs), represent promising modules for the bottom-up assembly of functional nanostructures. Here, we introduce the synthesis of a family of pyrene derivatives peripherally functionalized with pyridin-4-ylethynyl termini and comprehensively characterize their self-assembly abilities on a smooth Ag(111) support by scanning tunneling microscopy. By deliberate selection of number and geometric positioning of the pyridyl-terminated substituents, two-dimensional arrays, one-dimensional coordination chains, and chiral, porous kagomé-type networks can be tailored. A comparison to phenyl-functionalized reference pyrenes, not supporting the self-assembly of ordered structures at low coverage, highlights the role of the pyridyl moieties for supramolecular crocheting and knitting. Furthermore, we demonstrate the selective spangling of pores in the two-dimensional pyrene assemblies by a distinct number of iodine atoms as guests by atomically resolved imaging and complementary X-ray photoelectron spectroscopy.

A Bifunctional Electrocatalyst for Oxygen Evolution and Oxygen Reduction Reactions in Water.

Oxygen reduction and water oxidation are two key processes in fuel cell applications. The oxidation of water to dioxygen is a 4 H+/4 e- process, while oxygen can be fully reduced to water by a 4 e-/4 H+ process or partially reduced by fewer electrons to reactive oxygen species such as H2O2 and O2-. We demonstrate that a novel manganese corrole complex behaves as a bifunctional catalyst for both the electrocatalytic generation of dioxygen as well as the reduction of dioxygen in aqueous media. Furthermore, our combined kinetic, spectroscopic, and electrochemical study of manganese corroles adsorbed on different electrode materials (down to a submolecular level) reveals mechanistic details of the oxygen evolution and reduction processes.

Intermolecular Hybridization Creating Nanopore Orbital in a Supramolecular Hydrocarbon Sheet.

Molecular orbital engineering is a key ingredient for the design of organic devices. Intermolecular hybridization promises efficient charge carrier transport but usually requires dense packing for significant wave function overlap. Here we use scanning tunneling spectroscopy to spatially resolve the electronic structure of a surface-confined nanoporous supramolecular sheet of a prototypical hydrocarbon compound featuring terminal alkyne (-CCH) groups. Surprisingly, localized nanopore orbitals are observed, with their electron density centered in the cavities surrounded by the functional moieties. Density functional theory calculations reveal that these new electronic states originate from the intermolecular hybridization of six in-plane π-orbitals of the carbon-carbon triple bonds, exhibiting significant electronic splitting and an energy downshift of approximately 1 eV. Importantly, these nanopore states are distinct from previously reported interfacial states. We unravel the underlying connection between the formation of nanopore orbital and geometric arrangements of functional groups, thus demonstrating the generality of applying related orbital engineering concepts in various types of porous organic structures.

Surface-Guided Formation of an Organocobalt Complex.

Organocobalt complexes represent a versatile tool in organic synthesis as they are important intermediates in Pauson-Khand, Friedel-Crafts, and Nicholas reactions. Herein, a single-molecule-level investigation addressing the formation of an organocobalt complex at a solid-vacuum interface is reported. Deposition of 4,4'-(ethyne-1,2-diyl)dibenzonitrile and Co atoms on the Ag(111) surface followed by annealing resulted in genuine complexes in which single Co atoms laterally coordinated to two carbonitrile groups undergo organometallic bonding with the internal alkyne moiety of adjacent molecules. Alternative complexation scenarios involving fragmentation of the precursor were ruled out by complementary X-ray photoelectron spectroscopy. According to density functional theory analysis, the complexation with the alkyne moiety follows the Dewar-Chatt-Duncanson model for a two-electron-donor ligand where an alkyne-to-Co donation occurs together with a strong metal-to-alkyne back-donation.