Chiral Surface from Achiral Ingredients: Modification of Cu(110) with Phthalic Acid

The adsorption of dicarboxylic acids is a classical model approach for understanding molecular recognition at surfaces. The interaction of achiral phthalic acid with an achiral Cu(110) surface has been investigated in ultrahigh vacuum by means of scanning tunneling microscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy, reflection absorption infrared spectroscopy, temperature-programmed desorption, and density functional theory. Different ordered domains at a length scale of several tens of nanometers are observed, of which three are enantiomorphous and therefore appear in two mirror-symmetric forms. Theoretical considerations suggest that spontaneous mirror-symmetry breaking occurs at the single-molecular level, in which the surface becomes also chirally distorted

<i>Z</i>₃ Charge Density Wave of Silicon Atomic Chains on a Vicinal Silicon Surface

An ideal one-dimensional electronic system is formed along atomic chains on Au-decorated vicinal silicon surfaces, but the nature of its low-temperature phases has been puzzling for last two decades. Here, we unambiguously identify the low-temperature structural distortion of this surface using high-resolution atomic force microscopy and scanning tunneling microscopy. The most important structural ingredient of this surface, the step-edge Si chains, are found to be strongly buckled, every third atom down, forming trimer unit cells. This observation is consistent with the recent model of rehybridized dangling bonds and rules out the antiferromagnetic spin ordering proposed earlier. The spectroscopy and electronic structure calculation indicate a charge density wave insulator with a Z3 topology, making it possible to exploit topological phases and excitations. The tunneling current was found to substantially lower the energy barrier between three degenerate CDW states, which induces a dynamically fluctuating CDW at very low temperature

On-Surface Synthesis of Square-Type Porphyrin Tetramers with Central Antiaromatic Cyclooctatetraene Moiety

The synthesis of two-dimensionally extended polycyclic heteroatomic molecules keeps attracting considerable attention. In particular, frameworks bearing planar cyclooctatetraenes (COT) moieties can display intriguing properties, including antiaromaticity. Here, we present an on-surface chemistry route to square-type porphyrin tetramers with a central COT ring, coexisting with other oligomers. This approach employing temperature-induced dehydrogenative porphyrin homocoupling in an ultrahigh vacuum environment provides access to surface-supported, unsubstituted porphyrin tetramers that are not easily achievable by conventional synthesis means. Specifically, monomeric free-base (2H-P) and Zn-metalated (Zn-P) porphines (P) were employed to form square-type free-base and Zn-functionalized tetramers on Ag(100). An atomic-level characterization by bond-resolved atomic force microscopy and scanning tunneling microscopy and spectroscopy is provided, identifying the molecular structures. Complemented by density functional theory modeling, the electronic structure is elucidated, indeed revealing antiaromaticity induced by the COT moiety. The present study thus gives access, and insights, to a porphyrin oligomer, representing both a model system for directly fused porphyrins and a potential building block for conjugated, extended two-dimensional porphyrin sheets

Selective Activation of Aromatic C–H Bonds Catalyzed by Single Gold Atoms at Room Temperature

Selective activation and controlled functionalization of C–H bonds in organic molecules is one of the most desirable processes in synthetic chemistry. Despite progress in heterogeneous catalysis using metal surfaces, this goal remains challenging due to the stability of C–H bonds and their ubiquity in precursor molecules, hampering regioselectivity. Here, we examine the interaction between 9,10-dicyanoanthracene (DCA) molecules and Au adatoms on a Ag(111) surface at room temperature (RT). Characterization via low-temperature scanning tunneling microscopy, spectroscopy, and noncontact atomic force microscopy, supported by theoretical calculations, revealed the formation of organometallic DCA–Au–DCA dimers, where C atoms at the ends of the anthracene moieties are bonded covalently to single Au atoms. The formation of this organometallic compound is initiated by a regioselective cleaving of C–H bonds at RT. Hybrid quantum mechanics/molecular mechanics calculations show that this regioselective C–H bond cleaving is enabled by an intermediate metal–organic complex which significantly reduces the dissociation barrier of a specific C–H bond. Harnessing the catalytic activity of single metal atoms, this regioselective on-surface C–H activation reaction at RT offers promising routes for future synthesis of functional organic and organometallic materials

Characteristic Contrast in Δ<i>f</i>_min Maps of Organic Molecules Using Atomic Force Microscopy

Scanning tunneling microscopy and atomic force microscopy can provide detailed information about the geometric and electronic structure of molecules with submolecular spatial resolution. However, an essential capability to realize the full potential of these techniques for chemical applications is missing from the scanning probe toolbox: chemical recognition of organic molecules. Here, we show that maps of the minima of frequency shift–distance curves extracted from 3D data cubes contain characteristic contrast. A detailed theoretical analysis based on density functional theory and molecular mechanics shows that these features are characteristic for the investigated species. Structurally similar but chemically distinct molecules yield significantly different features. We find that the van der Waals and Pauli interaction, together with the specific adsorption geometry of a given molecule on the surface, accounts for the observed contrast

Tuning the Diradical Character of Pentacene Derivatives via Non-Benzenoid Coupling Motifs

The development of functional organic molecules requires structures of increasing size and complexity, which are typically obtained by the covalent coupling of smaller building blocks. Herein, with the aid of high-resolution scanning tunneling microscopy/spectroscopy and density functional theory, the coupling of a sterically demanded pentacene derivative on Au(111) into fused dimers connected by non-benzenoid rings was studied. The diradical character of the products was tuned according to the coupling section. In particular, the antiaromaticity of cyclobutadiene as the coupling motif and its position within the structure play a decisive role in shifting the natural orbital occupancies toward a stronger diradical electronic character. Understanding these structure–property relations is desirable not only for fundamental reasons but also for designing new complex and functional molecular structures