Stripe-Like hBN Monolayer Template for Self-Assembly and Alignment of Pentacene Molecules.

Metallic surfaces with unidirectional anisotropy are often used to guide the self-assembly of organic molecules along a particular direction. Such supports thus offer an avenue for the fabrication of hybrid organic-metal interfaces with tailored morphology and precise elemental composition. Nonetheless, such control often comes at the expense of detrimental interfacial interactions that might quench the pristine properties of molecules. Here, hexagonal boron nitride grown on Ir(100) is introduced as a robust platform with several coexisting 1D stripe-like moiré superstructures that effectively guide unidirectional self-assemblies of pentacene molecules, concomitantly preserving their pristine electronic properties. In particular, highly-aligned longitudinal arrays of equally-oriented molecules are formed along two perpendicular directions, as demonstrated by comprehensive scanning tunneling microscopy and photoemission characterization performed at the local and non-local scale, respectively. The functionality of the template is demonstrated by photoemission tomography, a surface-averaging technique requiring a high degree of orientational order of the probed molecules. The successful identification of pentacene's pristine frontier orbitals underlines that the template induces excellent long-range molecular ordering via weak interactions, preventing charge transfer.

Actinide Coordination Chemistry on Surfaces: Synthesis, Manipulation, and Properties of Thorium Bis(porphyrinato) Complexes.

Actinide-based metal-organic complexes and coordination architectures encompass intriguing properties and functionalities but are still largely unexplored on surfaces. We introduce the in situ synthesis of actinide tetrapyrrole complexes under ultrahigh-vacuum conditions, on both a metallic support and a 2D material. Specifically, exposure of a tetraphenylporphyrin (TPP) multilayer to an elemental beam of thorium followed by a temperature-programmed reaction and desorption of surplus molecules yields bis(porphyrinato)thorium (Th(TPP)2) assemblies on Ag(111) and hexagonal boron nitride/Cu(111). A multimethod characterization including X-ray photoelectron spectroscopy, scanning tunneling microscopy, temperature-programmed desorption, and complementary density functional theory modeling provides insights into conformational and electronic properties. Supramolecular assemblies of Th(TPP)2 as well as individual double-deckers are addressed with submolecular precision, e.g., demonstrating the reversible rotation of the top porphyrin in Th(TPP)2 by molecular manipulation. Our findings thus demonstrate prospects for actinide-based functional nanoarchitectures.

On-Surface Synthesis of Nonmetal Porphyrins.

We report the on-surface synthesis of a nonmetal porphyrin, namely, silicon tetraphenylporphyrin (Si-TPP), by the deposition of atomic silicon onto a free-base TPP layer on a Ag(100) surface under ultrahigh vacuum (UHV) conditions. Scanning tunneling microscopy provides insights into the self-assembly of the TPP molecules before and after Si insertion. Silicon coordinates with all four nitrogen atoms of the TPP macrocycle and interacts with a silver atom of the substrate as confirmed by scanning tunneling spectroscopy, X-ray photoelectron spectroscopy, and complementary density functional theory calculations. The Si-TPP complex presents a saddle-shaped conformation that is stable under STM manipulation. Our study shows how protocols established for the on-surface metalation of tetrapyrroles can be adopted to achieve nonmetal porphyrins. Complementary experiments yielding Si-TPP and Ge-TPP on Ag(111) highlight the applicability to different main group elements and supports. The success of our nonmetal porphyrin synthesis procedure is further corroborated by a temperature-programmed desorption experiment, revealing the desorption of Ge-TPP. This extension of interfacial complex formation beyond metal elements opens promising prospects for new tetrapyrrole architectures with distinct properties and functionalities.

Exploration of Interfacial Porphine Coupling Schemes and Hybrid Systems by Bond-Resolved Scanning Probe Microscopy.

The templated synthesis of porphyrin-based oligomers and heterosystems is of considerable interest for materials with tunable electronic gaps, photovoltaics, or sensing device elements. In this work, temperature-induced dehydrogenative coupling between unsubstituted free-base porphine units and their attachment to graphene nanoribbons on a well-defined Ag(111) support are scrutinized by bond-resolved scanning probe microscopy techniques. The detailed inspection of covalently fused porphine dimers obtained by in vacuo on-surface synthesis clearly reveals atomistic details of coupling motifs, whereby also putative reaction intermediates are identified. Moreover, the covalent attachment of porphines at preferred locations of atomically precise armchair-type graphene nanoribbons is demonstrated.

Tailoring Large Pores of Porphyrin Networks on Ag(111) by Metal-Organic Coordination.

The engineering of nanoarchitectures to achieve tailored properties relevant for macroscopic devices is a key motivation of organometallic surface science. To this end, understanding the role of molecular functionalities in structure formation and adatom coordination is of great importance. In this study, the differences in formation of Cu-mediated metal-organic coordination networks based on two pyridyl- and cyano-bearing free-base porphyrins on Ag(111) are elucidated by use of low-temperature scanning tunneling microscopy (STM). Distinct coordination networks evolve via different pathways upon codeposition of Cu adatoms. The cyano-terminated module directly forms 2D porous networks featuring fourfold-coordinated Cu nodes. By contrast, the pyridyl species engage in twofold coordination with Cu and a fully reticulated 2D network featuring a pore size exceeding 3 nm2 only evolves via an intermediate structure based on 1D coordination chains. The STM data and complementary Monte Carlo simulations reveal that these distinct network architectures originate from spatial constraints at the coordination centers. Cu adatoms are also shown to form two- and fourfold monoatomic coordination nodes with monotopic nitrogen-terminated linkers on the very same metal substrate-a versatility that is not achieved by other 3d transition metal centers but consistent with 3D coordination chemistry. This study discloses how specific molecular functionalities can be applied to tailor coordination architectures and highlights the potential of Cu as coordination center in such low-dimensional structures on surfaces.

Iron phthalocyanine on Cu(111): Coverage-dependent assembly and symmetry breaking, temperature-induced homocoupling, and modification of the adsorbate-surface interaction by annealing.

We have examined the geometric and electronic structures of iron phthalocyanine assemblies on a Cu(111) surface at different sub- to mono-layer coverages and the changes induced by thermal annealing at temperatures between 250 and 320 °C by scanning tunneling microscopy, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy. The symmetry breaking observed in scanning tunneling microscopy images is found to be coverage dependent and to persist upon annealing. Further, we find that annealing to temperatures between 300 and 320 °C leads to both desorption of iron phthalocyanine molecules from the surface and their agglomeration. We see clear evidence of temperature-induced homocoupling reactions of the iron phthalocyanine molecules following dehydrogenation of their isoindole rings, similar to what has been observed for related tetrapyrroles on transition metal surfaces. Finally, spectroscopy indicates a modified substrate-adsorbate interaction upon annealing with a shortened bond distance. This finding could potentially explain a changed reactivity of Cu-supported iron phthalocyanine in comparison to that of the pristine compound.

Surface-Assisted Cyclodehydrogenation; Break the Symmetry, Enhance the Selectivity.

Selectivity in chemical reactions is a major objective in industrial processes to minimize spurious byproducts and to save scarce resources. In homogeneous catalysis the most important factor which determines selectivity is structural symmetry. However, a transfer of the symmetry concept to heterogeneous catalysis still requires a detailed comprehension of the underlying processes. Here, we investigate a ring-closing reaction in surface-confined meso-substituted porphyrin molecules by scanning tunneling microscopy, temperature-programmed desorption, and computational modeling. The identification of reaction intermediates enables us to analyze the reaction pathway and to conclude that the symmetry of the porphyrin core is of pivotal importance regarding product yields.

Surface-assisted dehydrogenative homocoupling of porphine molecules.

The templated synthesis of porphyrin dimers, oligomers, and tapes has recently attracted considerable interest. Here, we introduce a clean, temperature-induced covalent dehydrogenative coupling mechanism between unsubstituted free-base porphine units yielding dimers, trimers, and larger oligomers directly on a Ag(111) support under ultrahigh-vacuum conditions. Our multitechnique approach, including scanning tunneling microscopy, near-edge X-ray absorption fine structure and photoelectron spectroscopy complemented by theoretical modeling, allows a comprehensive characterization of the resulting nanostructures and sheds light on the coupling mechanism. We identify distinct coupling motifs and report a decrease of the electronic gap and a modification of the frontier orbitals directly associated with the formation of triply fused dimeric species. This new on-surface homocoupling protocol yields covalent porphyrin nanostructures addressable with submolecular resolution and provides prospective model systems towards the exploration of extended oligomers with tailored chemical and physical properties.

Controlled interaction of surface quantum-well electronic states.

We report on the construction of well-defined surface quantum well arrangements by combining self-assembly protocols and molecular manipulation procedures. After the controlled removal of individual porphyrin molecules from dense-packed arrays on Ag(111), the surface state electrons are confined at the bare silver patches. These act as quantum wells that show well-defined unoccupied bound surface states. Scanning tunneling spectroscopy and complementary boundary element method calculations are performed to characterize the interaction between the bound states of adjacent quantum wells and reveal a hybridization of wave functions resulting in bonding and antibonding states. The interwell coupling can be tuned by the deliberate choice of the molecules acting as potential barriers. The fabrication method is shown to be ideally suited to engineer specific configurations as one-dimensional chains or two-dimensional artificial molecules.

Deceptive orbital confinement at edges and pores of carbon-based 1D and 2D nanoarchitectures.

The electronic structure defines the properties of graphene-based nanomaterials. Scanning tunneling microscopy/spectroscopy (STM/STS) experiments on graphene nanoribbons (GNRs), nanographenes, and nanoporous graphene (NPG) often determine an apparent electronic orbital confinement into the edges and nanopores, leading to dubious interpretations such as image potential states or super-atom molecular orbitals. We show that these measurements are subject to a wave function decay into the vacuum that masks the undisturbed electronic orbital shape. We use Au(111)-supported semiconducting gulf-type GNRs and NPGs as model systems fostering frontier orbitals that appear confined along the edges and nanopores in STS measurements. DFT calculations confirm that these states originate from valence and conduction bands. The deceptive electronic orbital confinement observed is caused by a loss of Fourier components, corresponding to states of high momentum. This effect can be generalized to other 1D and 2D carbon-based nanoarchitectures and is important for their use in catalysis and sensing applications.

Supramolecular assembly of interfacial nanoporous networks with simultaneous expression of metal-organic and organic-bonding motifs.

The formation of 2D surface-confined supramolecular porous networks is scientifically and technologically appealing, notably for hosting guest species and confinement phenomena. In this study, we report a scanning tunneling microscopy (STM) study of the self-assembly of a tripod molecule specifically equipped with pyridyl functional groups to steer a simultaneous expression of lateral pyridyl-pyridyl interactions and Cu-pyridyl coordination bonds. The assembly protocols yield a new class of porous open assemblies, the formation of which is driven by multiple interactions. The tripod forms a purely porous organic network on Ag(111), phase α, in which the presence of the pyridyl groups is crucial for porosity, as confirmed by molecular dynamics and Monte Carlo simulations. Additional deposition of Cu dramatically alters this scenario. For submonolayer coverage, three different porous phases coexist (i.e., ß, γ, and δ). Phases ß and γ are chiral and exhibit a simultaneous expression of lateral pyridyl-pyridyl interactions and twofold Cu-pyridyl linkages, whereas phase δ is just stabilized by twofold Cu-pyridyl bonds. An increase in the lateral molecular coverage results in a rise in molecular pressure, which leads to the formation of a new porous phase (ε), only coexisting with phase α and stabilized by a simultaneous expression of lateral pyridyl-pyridyl interactions and threefold Cu-pyridyl bonds. Our results will open new avenues to create complex porous networks on surfaces by exploiting components specifically designed for molecular recognition through multiple interactions.

Selective supramolecular fullerene-porphyrin interactions and switching in surface-confined C60-Ce(TPP)2 dyads.

The control of organic molecules, supramolecular complexes and donor-acceptor systems at interfaces is a key issue in the development of novel hybrid architectures for regulation of charge-carrier transport pathways in nanoelectronics or organic photovoltaics. However, at present little is known regarding the intricate features of stacked molecular nanostructures stabilized by noncovalent interactions. Here we explore at the single molecule level the geometry and electronic properties of model donor-acceptor dyads stabilized by van der Waals interactions on a single crystal Ag(111) support. Our combined scanning tunneling microscopy/spectroscopy (STM/STS) and first-principles computational modeling study reveals site-selective positioning of C(60) molecules on Ce(TPP)(2) porphyrin double-decker arrays with the fullerene centered on the π-system of the top bowl-shaped tetrapyrrole macrocycle. Three specific orientations of the C(60) cage in the van der Waals complex are identified that can be reversibly switched by STM manipulation protocols. Each configuration presents a distinct conductivity, which accounts for a tristable molecular switch and the tunability of the intradyad coupling. In addition, STS data evidence electronic decoupling of the hovering C(60) units from the metal substrate, a prerequisite for photophysical applications.

Boron nitride on Cu(111): an electronically corrugated monolayer.

Ultrathin films of boron nitride (BN) have recently attracted considerable interest given their successful incorporation in graphene nanodevices and their use as spacer layers to electronically decouple and order functional adsorbates. Here, we introduce a BN monolayer grown by chemical vapor deposition of borazine on a single crystal Cu support, representing a model system for an electronically patterned but topographically smooth substrate. Scanning tunneling microscopy and spectroscopy experiments evidence a weak bonding of the single BN sheet to Cu, preserving the insulating character of bulk hexagonal boron nitride, combined with a periodic lateral variation of the local work function and the surface potential. Complementary density functional theory calculations reveal a varying registry of the BN relative to the Cu lattice as origin of this electronic Moiré-like superstructure.

Formation of an Extended Quantum Dot Array Driven and Autoprotected by an Atom-Thick h-BN Layer.

Engineering quantum phenomena of two-dimensional nearly free electron states has been at the forefront of nanoscience studies ever since the first creation of a quantum corral. Common strategies to fabricate confining nanoarchitectures rely on manipulation or on applying supramolecular chemistry principles. The resulting nanostructures do not protect the engineered electronic states against external influences, hampering the potential for future applications. These restrictions could be overcome by passivating the nanostructures with a chemically inert layer. To this end we report a scalable segregation-based growth approach forming extended quasi-hexagonal nanoporous CuS networks on Cu(111) whose assembly is driven by an autoprotecting h-BN overlayer. We further demonstrate that by this architecture both the Cu(111) surface state and image potential states of the h-BN/CuS heterostructure are confined within the nanopores, effectively forming an extended array of quantum dots. Semiempirical electron-plane-wave-expansion simulations shed light on the scattering potential landscape responsible for the modulation of the electronic properties. The protective properties of the h-BN capping are tested under various conditions, representing an important step toward the realization of robust surface state based electronic devices.

The surface trans effect: influence of axial ligands on the surface chemical bonds of adsorbed metalloporphyrins.

The chemical bond between an adsorbed, laterally coordinated metal ion and a metal surface is affected by an additional axial ligand on the metal ion. This surface analogon of the trans effect was studied in detail using monolayers of various M(II)-tetraphenylporphyrins (MTTPs, M = Fe, Co, Zn) and their nitrosyl complexes on a Ag(111) surface. X-ray photoelectron spectroscopy (XPS) shows that the oxidation state of the Fe and Co (but not Zn) ions in the MTPP monolayers is reduced because of the interaction with the substrate. This partial reduction is accompanied by the appearance of new valence states in the UV photoelectron and scanning tunneling spectra (UPS and STS), revealing the covalent character of the ion-substrate bond. Subsequent coordination of nitric oxide (NO) to the metal ions (Fe, Co) reverses these surface-induced effects, resulting in an increase of the oxidation states and the disappearance of the new valence states. Removal of the NO ligands by thermal desorption restores the original spectroscopic features, indicating that the described processes are fully reversible. The NO coordination also changes the spin state and thus the magnetic properties of the metal ions. Density-functional theory (DFT) calculations on model systems provide structural and energetic data on the adsorbed molecules and the surface chemical bond. The calculations reveal that competition effects, similar to the trans effect, play a central role and lead to a mutual interference of the two axial ligands, NO and Ag, and their bonds to the metal center. These findings have important implications for sensor technology and catalysis using supported planar metal complexes, in which the activity of the metal center is sensitively influenced by the substrate.

Ensemble modeling of very small ZnO nanoparticles.

The detailed structural characterization of nanoparticles is a very important issue since it enables a precise understanding of their electronic, optical and magnetic properties. Here we introduce a new method for modeling the structure of very small particles by means of powder X-ray diffraction. Using thioglycerol-capped ZnO nanoparticles with a diameter of less than 3 nm as an example we demonstrate that our ensemble modeling method is superior to standard XRD methods like, e.g., Rietveld refinement. Besides fundamental properties (size, anisotropic shape and atomic structure) more sophisticated properties like imperfections in the lattice, a size distribution as well as strain and relaxation effects in the particles and-in particular-at their surface (surface relaxation effects) can be obtained. Ensemble properties, i.e., distributions of the particle size and other properties, can also be investigated which makes this method superior to imaging techniques like (high resolution) transmission electron microscopy or atomic force microscopy, in particular for very small nanoparticles. For the particles under study an excellent agreement of calculated and experimental X-ray diffraction patterns could be obtained with an ensemble of anisotropic polyhedral particles of three dominant sizes, wurtzite structure and a significant relaxation of Zn atoms close to the surface.

Surface-assisted assembly of discrete porphyrin-based cyclic supramolecules.

We employed de novo synthesized porphyrin modules to construct discrete cyclic supramolecular architectures supported on a copper surface. The programmed geometry and functionality of the molecular modules together with their conformational flexibility and substrate interaction yields symmetric discrete assemblies, including dimers and chains as well as three- to six-membered cyclic structures. The area of the molecular cavities is extended by creating bicomponent structures combining building blocks with different symmetry.

Borophenes made easy.

To date, the scalable synthesis of elemental two-dimensional materials beyond graphene still remains elusive. Here, we introduce a versatile chemical vapor deposition (CVD) method to grow borophenes, as well as borophene heterostructures, by selectively using diborane originating from traceable byproducts of borazine. Specifically, metallic borophene polymorphs were successfully synthesized on Ir(111) and Cu(111) single-crystal substrates and conjointly with insulating hexagonal boron nitride (hBN) to form atomically precise lateral borophene-hBN interfaces or vertical van der Waals heterostructures. Thereby, borophene is protected from immediate oxidation by a single hBN overlayer. The ability to synthesize high-quality borophenes with large single-crystalline domains in the micrometer scale by a straight-forward CVD approach opens up opportunities for the study of their fundamental properties and for device incorporation.

Discriminative response of surface-confined metalloporphyrin molecules to carbon and nitrogen monoxide.

The binding of small gas molecules to metalloporphyrins is of both fundamental scientific and technological interest. It plays a key role in the transport of respiratory gases, catalytic processes in biological systems, and artificial nanostructures for sensing. Here, we present a detailed molecular-level investigation regarding the interaction of nitrogen monoxide (NO) and carbon monoxide (CO) with metallo-tetraphenylporphyrin (M-TPP, M = Co, Fe) arrays, anchored on a noble metal Ag(111) surface, providing M-TPP species with a distinct saddle-shape conformation. Scanning tunneling microscopy and spectroscopy experiments reveal that the impact of CO and NO is strikingly different on both species. In the case of CO, the M-TPP core can be dressed by either one or two carbon monoxide ligands, whereby the porphyrin geometric and electronic structure remains nearly unaffected. In contrast, following NO exposure exclusively a mononitrosyl species evolves. The NO axial ligation induces a relaxation of the adsorption-induced molecular deformation and markedly modifies the electronic structure of the porphyrin.

Self-assembly of flexible one-dimensional coordination polymers on metal surfaces.

We employed a de novo synthesized porphyrin module to construct one-dimensional (1D) Cu-coordinated polymers on Cu(111) and Ag(111) surfaces. The programmed geometry and functionality of the molecular module together with its conformational flexibility and substrate interaction yields sinuous metal-organic polymeric assemblies, based on an unusual two-fold Cu-pyridyl coordination motif. An analysis of scanning tunneling microscopy (STM) data reveals the occurrence of two enantiomers, resulting from the surface confinement that deconvolutes the module in 2D-chiral conformational isomers. The stereoisomers exhibit site-specific surface anchoring, from whence three discrete orientations are possible for each species. Their sequence and mutual arrangement determine direction and curvature of the metal-organic chains. The Cu-coordinated polymers are very similar on both Cu(111) and Ag(111), where their formation is induced by intrinsic and coevaporated adatoms, respectively, which indicates that the lateral bonding motif is predominantly independent of the substrate. In addition, molecular manipulation experiments show the collective motion of entire segments of the Cu-coordinated multi-porphyrin polymers.