Search

Surface-catalyzed reactions have been used to synthesize carbon nanomaterials with atomically predefined structures. The recent discovery of a gold surface-catalyzed [3 + 3] cycloaromatization of isopropyl substituted arenes has enabled the on-surface synthesis of arylene-phenylene copolymers, where the surface activates the isopropyl substituents to form phenylene rings by intermolecular coupling. However, the resulting polymers suffered from undesired cross-linking when more than two molecules reacted at a single site. Here we show that such cross-links can be prevented through steric protection by attaching the isopropyl groups to larger arene cores. Upon thermal activation of isopropyl-substituted 8,9-dioxa-8a-borabenzo[ fg ]tetracene on Au(111), cycloaromatization is observed to occur exclusively between the two molecules. The cycloaromatization intermediate formed by the covalent linking of two molecules is prevented from reacting with further molecules by the wide benzotetracene core, resulting in highly selective one-to-one coupling. Our findings extend the versatility of the [3 + 3] cycloaromatization of isopropyl substituents and point toward steric protection as a powerful concept for suppressing competing reaction pathways in on-surface synthesis., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The design of open-shell carbon-based nanomaterials is at the vanguard of materials science, steered by their beneficial magnetic properties like weaker spin-orbit coupling than that of transition metal atoms and larger spin delocalization, which are of potential relevance for future spintronics and quantum technologies. A key parameter in magnetic materials is the magnetic exchange coupling (MEC) between unpaired spins, which should be large enough to allow device operation at practical temperatures. In this work, we theoretically and experimentally explore three distinct families of nanographenes (NGs) ( A , B , and C ) featuring majority zigzag peripheries. Through many-body calculations, we identify a transition from a closed-shell ground state to an open-shell ground state upon an increase of the molecular size. Our predictions indicate that the largest MEC for open-shell NGs occurs in proximity to the transition between closed-shell and open-shell states. Such predictions are corroborated by the on-surface syntheses and structural, electronic, and magnetic characterizations of three NGs ( A[3,5] , B[4,5] , and C[4,3] ), which are the smallest open-shell systems in their respective chemical families and are thus located the closest to the transition boundary. Notably, two of the NGs ( B[4,5] and C[4,3] ) feature record values of MEC (close to 200 meV) measured on the Au(111) surface. Our strategy for maximizing the MEC provides perspectives for designing carbon nanomaterials with robust magnetic ground states.

The design of antiferromagnetic nanomaterials preserving large orbital magnetic moments is important to protect their functionalities against magnetic perturbations. Here, we exploit an archetype H 6 HOTP species for conductive metal-organic frameworks to design a Co-HOTP one-atom-thick metal-organic architecture on a Au(111) surface. Our multidisciplinary scanning probe microscopy, X-ray absorption spectroscopy, X-ray linear dichroism, and X-ray magnetic circular dichroism study, combined with density functional theory simulations, reveals the formation of a unique network design based on threefold Co +2 coordination with deprotonated ligands, which displays a large orbital magnetic moment with an orbital to effective spin moment ratio of 0.8, an in-plane easy axis of magnetization, and large magnetic anisotropy. Our simulations suggest an antiferromagnetic ground state, which is compatible with the experimental findings. Such a Co-HOTP metal-organic network exemplifies how on-surface chemistry can enable the design of field-robust antiferromagnetic materials.

The synthesis of novel polymeric materials with porphyrinoid compounds as key components of the repeating units attracts widespread interest from several scientific fields in view of their extraordinary variety of functional properties with potential applications in a wide range of highly significant technologies. The vast majority of such polymers present a closed-shell ground state, and, only recently, as the result of improved synthetic strategies, the engineering of open-shell porphyrinoid polymers with spin delocalization along the conjugation length has been achieved. Here, we present a combined strategy toward the fabrication of one-dimensional porphyrinoid-based polymers homocoupled via surface-catalyzed [3 + 3] cycloaromatization of isopropyl substituents on Au(111). Scanning tunneling microscopy and noncontact atomic force microscopy describe the thermal-activated intra- and intermolecular oxidative ring closure reactions as well as the controlled tip-induced hydrogen dissociation from the porphyrinoid units. In addition, scanning tunneling spectroscopy measurements, complemented by computational investigations, reveal the open-shell character, that is, the antiferromagnetic singlet ground state ( S = 0) of the formed polymers, characterized by singlet-triplet inelastic excitations observed between spins of adjacent porphyrinoid units. Our approach sheds light on the crucial relevance of the π-conjugation in the correlations between spins, while expanding the on-surface synthesis toolbox and opening avenues toward the synthesis of innovative functional nanomaterials with prospects in carbon-based spintronics.

Polycyclic aromatic hydrocarbons (PAHs) are a family of organic compounds comprising two or more fused aromatic rings which feature manifold applications in modern technology. Among these species, those presenting an open-shell magnetic ground state are of particular interest for organic electronic, spintronic, and non-linear optics and energy storage devices. Within PAHs, special attention has been devoted in recent years to the synthesis and study of the acene and fused acene (periacene) families, steered by their decreasing HOMO-LUMO gap with length and predicted open-shell character above some size. However, an experimental fingerprint of such magnetic ground state has remained elusive. Here, we report on the in-depth electronic characterization of isolated peripentacene molecules on a Au(111) surface. Scanning tunnelling spectroscopy, complemented by computational investigations, reveals an antiferromagnetic singlet ground state, characterized by singlet-triplet inelastic excitations with an experimental effective exchange coupling ( J eff ) of 40.5 meV. Our results deepen the fundamental understanding of organic compounds with magnetic ground states, featuring perspectives in carbon-based spintronic devices.

Nanographenes (NGs) have gained increasing attention due to their immense potential as tailor-made organic materials for nanoelectronics and spintronics. They exhibit a rich spectrum of physicochemical properties that can be tuned by controlling the size or the edge structure or by introducing structural defects in the honeycomb lattice. Here, we report the design and on-surface synthesis of NGs containing several odd-membered polycycles induced by a thermal procedure on Au(111). Our scanning tunneling microscopy, noncontact atomic force microscopy, and scanning tunneling spectroscopy measurements, complemented by computational investigations, describe the formation of two nonbenzenoid NGs ( 2A , B ) containing four embedded azulene units in the polycyclic framework, via on-surface oxidative ring-closure reactions. Interestingly, we observe surface-catalyzed skeletal ring rearrangement reactions in the NGs, which lead to the formation of additional heptagonal rings as well as pentalene and as -indacene units in 2A , B , respectively. 2A , B on Au(111) both exhibit narrow experimental frontier electronic gaps of 0.96 and 0.85 eV, respectively, and Fermi level pinning of their HOMOs together with considerable electron transfer to the substrate. Ab initio calculations estimate moderate open-shell biradical characters for the NGs in the gas phase.

Fully conjugated ladder polymers (CLP) possess unique optical and electronic properties and are considered promising materials for applications in (opto)electronic devices. Poly(indenoindene) is a CLP consisting of an alternating array of five- and six-membered rings, which has remained elusive so far. Here, we report an on-surface synthesis of oligo(indenoindene) on Au(111). Its structure and a low electronic band gap have been elucidated by low-temperature scanning tunneling microscopy and spectroscopy and noncontact atomic force microscopy, complemented by density functional theory calculations. Achieving defect-free segments of oligo(indenoindene) offers exclusive insight into this CLP and provides the basis to further synthetic approaches.

Coronoids, polycyclic aromatic hydrocarbons with geometrically defined cavities, are promising model structures of porous graphene. Here, we report the on-surface synthesis of C168 and C140 coronoids, referred to as [6]- and [5]coronoid, respectively, using 5,9-dibromo-14-phenylbenzo[ m ]tetraphene as the precursor. These coronoids entail large cavities (>1 nm) with inner zigzag edges, distinct from their outer armchair edges. While [6]coronoid is planar, [5]coronoid is not. Low-temperature scanning tunneling microscopy/spectroscopy and noncontact atomic force microscopy unveil structural and electronic properties in accordance with those obtained from density functional theory calculations. Detailed analysis of ring current effects identifies the rings with the highest aromaticity of these coronoids, whose pattern matches their Clar structure. The pores of the obtained coronoids offer intriguing possibilities of further functionalization toward advanced host-guest applications.

Multiple fused pentagon-heptagon pairs are frequently found as defects at the grain boundaries of the hexagonal graphene lattice and are suggested to have a fundamental influence on graphene-related materials. However, the construction of sp 2 -carbon skeletons with multiple regularly fused pentagon-heptagon pairs is challenging. In this work, we found that the pentagon-heptagon skeleton of azulene was rearranged during the thermal reaction of an azulene-incorporated organometallic polymer on Au(111). The resulting sp 2 -carbon frameworks were characterized by high-resolution scanning probe microscopy techniques and feature novel polycyclic architectures composed of multiple regularly fused pentagon-heptagon pairs. Moreover, the calculated analysis of its aromaticity revealed a peculiar polar electronic structure.

On-surface synthesis under ultrahigh vacuum conditions is a powerful tool to achieve molecular structures that cannot be accessed via traditional wet chemistry. Nevertheless, only a very limited number of chemical reactions out of the wide variety known from solution chemistry have been reported to proceed readily on atomically flat substrates. Cycloadditions are a class of reactions that are particularly important in the synthesis of sp 2 -hybridized carbon-based nanostructures. Here, we report on a specific type of [4 + 2] cycloaddition, namely, a dehydro-Diels-Alder (DDA) reaction, performed between bis(phenylethynyl)-benzene precursors on Au(111). Unlike a Diels-Alder reaction, DDA exploits ethynyl groups to achieve the formation of an extra six-membered ring. Despite its extensive use in solution chemistry for more than a century, this reaction has never been reported to occur on surfaces. The specific choice of our precursor molecule has led to the successful synthesis of benzo- and naphtho-fused tetracene and heptacene products bearing styryl groups, as confirmed by scanning tunneling microscopy and noncontact atomic force microscopy. The two products arise from dimerization and trimerization of the precursor molecules, respectively, and their observation opens perspectives to use DDA reactions as a novel on-surface synthesis tool.

The on-surface reactions of 10-bromo-10'-(2,6-dimethylphenyl)-9,9'-bianthracene on Au(111) have been investigated by scanning tunneling microscopy and spectroscopy, complemented by theoretical calculations. The reactions afford the synthesis of two open-shell nanographenes ( 1a and 1b ) exhibiting different scenarios of all-carbon magnetism. 1a , an all-benzenoid nanographene with triangulene-like termini, contains a high proportion of zigzag edges which endows it with a low frontier gap and edge-localized states. The dominant reaction product, 1b , is a non-benzenoid nanographene consisting of a single pentagonal ring in a benzenoid framework. The presence of this non-benzenoid topological defect, which alters the bond connectivity in the hexagonal lattice, results in a non-Kekulé nanographene with an unpaired spin, which is detected as a Kondo resonance.

We report the investigation of a conjugated polycyclic hydrocarbon containing multiple nonbenzenoid rings and exhibiting negative curvature-the warped nanographene C 80 H 30 -adsorbed on several noble metal surfaces in an ultrahigh vacuum environment. From a detailed analysis of the molecular self-assembly at different molecular coverages via scanning tunneling microscopy and spectroscopy measurements in combination with theoretical modeling, the nature of the intermolecular interactions is unraveled. For high molecular coverages on Cu(111), the formation of homochiral porous networks is observed, which is rationalized by (i) intermolecular π-π interactions between neighboring C 80 H 30 molecules that promote the formation of molecular dimers and (ii) enantioselective intermolecular CH···π interactions between the dimers. Such interactions are also observed after deposition of C 80 H 30 molecules on Au(111) and Ag(111) substrates. Our results provide perspectives for the on-surface study of negatively curved nanographenes which open new avenues to the design of novel and functional chiral structures with potential use in the field of organic optoelectronics.

Polycyclic hydrocarbons have received great attention due to their potential role in organic electronics and, for open-shell systems with unpaired electron densities, in spintronics and data storage. However, the intrinsic instability of polyradical hydrocarbons severely limits detailed investigations of their electronic structure. Here, we report the on-surface synthesis of conjugated polymers consisting of indeno[2,1- b ]fluorene units, which are antiaromatic and open-shell biradicaloids. The observed reaction products, which also include a nonbenzenoid porous ribbon arising from lateral fusion of unprotected indeno[2,1- b ]fluorene chains, have been characterized via low-temperature scanning tunneling microscopy/spectroscopy and noncontact atomic force microscopy, complemented by density-functional theory calculations. These polymers present a low band gap when adsorbed on Au(111). Moreover, their pronounced antiaromaticity and radical character, elucidated by ab initio calculations, make them promising candidates for applications in electronics and spintronics. Further, they provide a rich playground to explore magnetism in low-dimensional organic nanomaterials.

Nonbenzenoid carbocyclic rings are postulated to serve as important structural elements toward tuning the chemical and electronic properties of extended polycyclic aromatic hydrocarbons (PAHs, or namely nanographenes), necessitating a rational and atomically precise synthetic approach toward their fabrication. Here, using a combined bottom-up in-solution and on-surface synthetic approach, we report the synthesis of nonbenzenoid open-shell nanographenes containing two pairs of embedded pentagonal and heptagonal rings. Extensive characterization of the resultant nanographene in solution shows a low optical gap, and an open-shell singlet ground state with a low singlet-triplet gap. Employing ultra-high-resolution scanning tunneling microscopy and spectroscopy, we conduct atomic-scale structural and electronic studies on a cyclopenta-fused derivative on a Au(111) surface. The resultant five to seven rings embedded nanographene displays an extremely narrow energy gap of 0.27 eV and exhibits a pronounced open-shell biradical character close to 1 ( y 0 = 0.92). Our experimental results are supported by mean-field and multiconfigurational quantum chemical calculations. Access to large nanographenes with a combination of nonbenzenoid topologies and open-shell character should have wide implications in harnessing new functionalities toward the realization of future organic electronic and spintronic devices.

On-surface synthesis provides an effective approach toward the formation of graphene nanostructures that are difficult to achieve via traditional solution chemistry. Here, we report on the design and synthesis of a nonplanar porous nanographene with 78 sp 2 carbon atoms, namely C78. Through a highly selective oxidative cyclodehydrogenation of 2,3,6,7,10,11-hexa(naphthalen-1-yl)triphenylene (2), propeller nanographene precursor 1 was synthesized in solution. Interestingly, although 1 could not be cyclized further in solution, porous nanographene C78 was successfully achieved from 1 by on-surface assisted cyclodehydrogenation on Au(111). The structure and electronic properties of C78 have been investigated by means of scanning tunneling microscopy, noncontact atomic force microscopy, and scanning tunneling spectroscopy, complemented by computational investigations. Our results provide perspectives for the on-surface synthesis of porous graphene nanostructures, offering a promising strategy for the engineering of graphene materials with tailor-made properties.

Polycyclic aromatic hydrocarbons exhibit a rich spectrum of physicochemical properties depending on the size and, more critically, on the edge and bond topologies. Among them, open-shell systems-molecules hosting unpaired electron densities-represent an important class of materials for organic electronic, spintronic, and optoelectronic devices, but remain challenging to synthesize in solution. We report the on-surface synthesis and scanning tunneling microscopy- and spectroscopy-based study of two ultralow-gap open-shell molecules, namely peri-tetracene, a benzenoid graphene fragment with zigzag edge topology, and dibenzo[ a, m]dicyclohepta[ bcde, nopq]rubicene, a nonbenzenoid nonalternant structural isomer of peri-tetracene with two embedded azulene units. Our results provide an understanding of the ramifications of altered bond topologies at the single-molecule scale, with the prospect of designing functionalities in carbon-based nanostructures via engineering of bond topology.

Bottom-up synthesis of graphene nanoribbons (GNRs) has significantly advanced during the past decade, providing various GNR structures with tunable properties. The synthesis of chiral GNRs, however, has been underexplored and only limited to (3,1)-GNRs. We report herein the surface-assisted synthesis of the first heteroatom-doped chiral (4,1)-GNRs from the rationally designed precursor 6,16-dibromo-9,10,19,20-tetraoxa-9a,19a-diboratetrabenzo[ a, f, j, o]perylene. The structure of the chiral GNRs has been verified by scanning tunneling microscopy, noncontact atomic force microscopy, and Raman spectroscopy in combination with theoretical modeling. Due to the presence of oxygen-boron-oxygen (OBO) segments on the edges, lateral self-assembly of the GNRs has been observed, realizing well-aligned GNR arrays with different modes of homochiral and heterochiral inter-ribbon assemblies.

On-surface synthesis is a successful approach to the creation of carbon-based nanostructures that cannot be obtained via standard solution chemistry. In this framework, we have established a novel synthetic pathway to one-dimensional conjugated polymers composed of indenofluorene units. Our concept is based on the use of ortho-methyl groups on a poly( para-phenylene) backbone. In this situation, surface-assisted oxidative ring closure between a methyl and the neighboring aryl moiety gives rise to a five-membered ring. The atomically precise structures and electronic properties of the obtained indenofluorene polymers have been unambiguously characterized by STM, nc-AFM, and STS, supported by theoretical calculations. This unprecedented synthetic protocol can potentially be extended to other polyphenylenes and eventually graphene nanoribbons, to incorporate five-membered rings at desired positions for the fine-tuning of electronic properties.

Metallo-supramolecular engineering on surfaces provides a powerful strategy toward low-dimensional coordination architectures with prospects for several application fields. To date, most efforts have relied on transition metal centers, and only recently did we pioneer lanthanide-directed assembly. Coordination spheres and motifs with rare-earth elements generally display distinct properties and structural features. The size of the cations and shielding role of the 4f orbitals induces high coordination numbers, frequently entailing flexible coordination geometries. Following Pearson's hard and soft acid-base theory, lanthanide cations are hard Lewis acids and thus feature strong affinity for nitrile, terpyridine, and carboxylate donor moieties. The prevailing oxidation state is +3, although in certain compounds stable +2 or +4 cations occur. The chemistry of rare-earth elements is currently receiving widespread attention, as they are key ingredients for established and emerging 21st century science and technology with relevance for energy conversion, sensing, catalysis, magnetism, photonics, telecommunications, superconductivity, biomedicine, and quantum engineering. In this Account, we review recent advances toward the design of interfacial supramolecular nanoarchitectures incorporating lanthanide centers. We apply controlled ultrahigh vacuum conditions whereby atomistically clean substrates are prepared and exposed to ultrapure atomic and molecular beams of the chosen sublimable constituents. We focus on direct molecular-level investigations and in situ assembly operative close to equilibrium conditions. Our scanning probe microscopy techniques provide atomistic insights regarding the formation, stability, and manipulability of metal-organic compounds and networks. In order to gain deeper insights into the experimental findings, complementary computational analysis of bond characteristics, electronic properties, and coordination motifs has been performed for several case studies. Exemplary elements under consideration include cerium, gadolinium, dysprosium, and europium. By the use of ditopic molecular linkers equipped with carbonitrile moieties, adaptive coordination spheres are unveiled, yielding vertices with two- to sixfold symmetry. The respective coordination nodes underlie the expression of complex networks, such as semiregular Archimedean tessellations for cerium- or gadolinium-directed assemblies and random-tiling quasicrystalline characteristics for europium. Tunability via constituent stoichiometry regulation is revealed for bimolecular arrangements embedding europium centers, simultaneously connecting to carbonitrile and terypyridine ligands. Ditopic carboxylate linkers yield robust reticular networks based on a lateral coordination number of 8 for either gadolinium or dysprosium complexation, featuring a prevalent ionic nature of the coordination bond. Orthogonal insertion protocols give rise to d-f reticular architectures exploiting macrocyclic tetradentate cobalt complexation and peripheral carbonitrile-gadolinium coordination, respectively. Furthermore, lanthanides may afford metalation of adsorbed free-base tetrapyrrole species and can be engaged for interfacial synthesis of sandwich compounds, thus providing prospects for columnar design of coordination architectures. Finally, direct manipulation experiments achieved lateral displacement of single supramolecules and molecular rotation of sandwich or other molecular units. These findings evidence prospects for advancing molecular machinery components. The presented accomplishements herald further advancements in metallo-supramolecular design on surfaces, with versatile nanosystems and architectures emanating from the flexible coordination spheres. The embedding and systematic rationalization of lanthanide centers in tailored interfacial environments are keys to establishing relations between structure and physicochemical characteristics toward the generation of novel functionalities with technological significance.

On-surface synthesis is a powerful route toward the fabrication of specific graphene-like nanostructures confined in two dimensions. This strategy has been successfully applied to the growth of graphene nanoribbons of diverse width and edge morphology. Here, we investigate the mechanisms driving the growth of 9-atom wide armchair graphene nanoribbons by using scanning tunneling microscopy, fast X-ray photoelectron spectroscopy, and temperature-programmed desorption techniques. Particular attention is given to the role of halogen functionalization (Br or I) of the molecular precursors. We show that the use of iodine-containing monomers fosters the growth of longer graphene nanoribbons (average length of 45 nm) due to a larger separation of the polymerization and cyclodehydrogenation temperatures. Detailed insight into the growth process is obtained by analysis of kinetic curves extracted from the fast X-ray photoelectron spectroscopy data. Our study provides fundamental details of relevance to the production of future electronic devices and highlights the importance of not only the rational design of molecular precursors but also the most suitable reaction pathways to achieve the desired final structures.

We report the on-surface formation of Au-directed heptacene organometallic complexes on a Au(111) template in an ultrahigh vacuum environment. Successive thermal annealing steps investigated by means of scanning tunneling microscopy, noncontact atomic force microscopy, temperature-programmed desorption and density functional theory reveal the formation of heptacene organometallic complexes via a selective two-step activation of an α-diketone-protected heptacene precursor. Furthermore, we demonstrate the efficiency of tip-induced deprotection experiments as a complementary strategy in the complex formation. Our results provide perspectives for the on-surface synthesis of larger acenes featuring potential use in the fields of organic electronics, spintronics and nonlinear optics.

We report on the surface-assisted synthesis and spectroscopic characterization of the hitherto longest periacene analogue with oxygen-boron-oxygen (OBO) segments along the zigzag edges, that is, a heteroatom-doped perihexacene 1. Surface-catalyzed cyclodehydrogenation successfully transformed the double helicene precursor 2, i.e., 12a,26a-dibora-12,13,26,27-tetraoxa-benzo[1,2,3-hi:4,5,6-h'i']dihexacene, into the planar perihexacene analogue 1, which was visualized by scanning tunneling microscopy and noncontact atomic force microscopy. X-ray photoelectron spectroscopy, Raman spectroscopy, together with theoretical modeling, on both precursor 2 and product 1, provided further insights into the cyclodehydrogenation process. Moreover, the nonplanar precursor 2 underwent a conformational change upon adsorption on surfaces, and one-dimensional self-assembled superstructures were observed for both 2 and 1 due to the presence of OBO units along the zigzag edges.

We report the formation of a metal-organic network on a BN/Cu(111) template by codeposition of carbonitrile-functionalized porphyrin derivatives (2H-TPCN) with Co atoms in an ultrahigh vacuum environment. The resulting metallo-supramolecular structure explored by scanning tunneling microscopy and spectroscopy features a distinct 4-fold coordination motif. Furthermore, we demonstrate an in situ metalation of the tetrapyrrole macrocycles with deposited Co atoms yielding Co-TPCN directly on the BN sheet. Our results provide perspectives for the formation of coordination networks on BN and related systems featuring structural, electronic, and magnetic properties unachievable on metallic supports.

Coordination bonding between para-quarterphenyl-dicarbonitrile linkers and gadolinium on Ag(111) has been exploited to construct pentameric mononuclear supramolecules, consisting of a rare-earth center surrounded by five molecular linkers. By employing a scanning tunneling microscope tip, a manipulation protocol was developed to position individual pentamers on the surface. In addition, the tip was used to extract and replace individual linkers yielding tetrameric, pentameric, nonameric, and dodecameric metallosupramolecular arrangements. These results open new avenues toward advanced nanofabrication methods and rare-earth nanochemistry by combining the versatility of metal-ligand interactions and atomistic manipulation capabilities.

Suitable templates to steer the formation of nanostructure arrays on surfaces are indispensable in nanoscience. Recently, atomically thin sp(2)-bonded layers such as graphene or boron nitride (BN) grown on metal supports have attracted considerable interest due to their potential geometric corrugation guiding the positioning of atoms, metallic clusters or molecules. Here, we demonstrate three specific functions of a geometrically smooth, but electronically corrugated, sp(2)/metal interface, namely, BN/Cu(111), qualifying it as a unique nanoscale template. As functional adsorbates we employed free-base porphine (2H-P), a prototype tetrapyrrole compound, and tetracyanoquinodimethane (TCNQ), a well-known electron acceptor. (i) The electronic moirons of the BN/Cu(111) interface trap both 2H-P and TCNQ, steering self-organized growth of arrays with extended molecular assemblies. (ii) We report an effective decoupling of the trapped molecules from the underlying metal support by the BN, which allows for a direct visualization of frontier orbitals by scanning tunneling microscopy (STM). (iii) The lateral molecular positioning in the superstructured surface determines the energetic level alignment; i.e., the energy of the frontier orbitals, and the electronic gap are tunable.