Damian Nieckarz

On-surface Ullmann coupling: the influence of kinetic reaction parameters on the morphology and quality of covalent networks.

On-surface Ullmann coupling is a versatile and appropriate approach for the bottom-up fabrication of covalent organic nanostructures. In two-dimensional networks, however, the kinetically controlled and irreversible coupling leads to high defect densities and a lack of long-range order. To derive general guidelines for optimizing reaction parameters, the structural quality of 2D porous covalent networks was evaluated for different preparation protocols. For this purpose, polymerization of an iodine- and bromine-functionalized precursor was studied on Au(111) by scanning tunneling microscopy under ultrahigh vacuum conditions. By taking advantage of the vastly different temperature thresholds for C-Br and C-I cleavage, two different polymerization routes were compared - hierarchical and direct polymerization. The structural quality of the covalent networks was evaluated for different reaction parameters, such as surface temperatures, heating rates, and deposition rates by statistical analysis of STM data. Experimental results are compared to Monte Carlo simulations.

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., β, γ, and δ). Phases β 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.

Growth of covalently bonded Sierpiński triangles up to the second generation

Growth of covalently bonded Sierpinski triangles (CB-STs) on metal surfaces was investigated by scanning tunneling microscopy (STM). Three synthetic strategies (namely, dehydration condensation, cyclotrimerization coupling and Schiff-base reactions) were used to fabricate CB-STs. Second-generation CB-STs were obtained at the solid–vacuum interface utilizing the Schiff-base reaction between 4,4′′-dialdehyde-1,1′:3′,1′′-terphenyl (TPDAL) and 1,3,5-tris(4-aminophenyl)benzene (TAPB) on Au(111). The CB-ST patterns persist at annealing temperatures as high as 500 K. Homotactic three-fold motifs, insufficient migration and irreversible covalent reaction are the main limitations for growing higher-generation STs. The present results provide new insights on the growth of STs on metal surfaces.

From Au–Thiolate Chains to Thioether Sierpiński Triangles: The Versatile Surface Chemistry of 1,3,5-Tris(4-mercaptophenyl)benzene on Au(111)

Self-assembly of 1,3,5-tris(4-mercaptophenyl)benzene (TMB), a 3-fold symmetric, thiol-functionalized aromatic molecule, was studied on Au(111) with the aim of realizing extended Au-thiolate-linked molecular architectures. The focus lay on resolving thermally activated structural and chemical changes by a combination of microscopy and spectroscopy. Thus, scanning tunneling microscopy (STM) provided submolecularly resolved structural information, while the chemical state of sulfur was assessed by X-ray photoelectron spectroscopy (XPS). Directly after room-temperature deposition, only less well ordered structures were observed. Mild annealing promoted the first structural transition into ordered molecular chains, partly organized in homochiral molecular braids. Further annealing led to self-similar Sierpiński triangles, while annealing at even higher temperatures again resulted in mostly disordered structures. Both the irregular aggregates observed at room temperature and the chains were identified as metal-organic assemblies, whereby two out of the three intermolecular binding motifs are energetically equivalent according to density functional theory (DFT) simulations. The emergence of Sierpiński triangles is driven by a chemical transformation, i.e., the conversion of coordinative Au-thiolate to covalent thioether linkages, and can be further understood by Monte Carlo simulations. The great structural variance of TMB on Au(111) can on one hand be explained by the energetic equivalence of two binding motifs. On the other hand, the unexpected chemical transition even enhances the structural variance and results in thiol-derived covalent molecular architectures.

Influence of Relativistic Effects on Assembled Structures of V-Shaped Bispyridine Molecules on M(111) Surfaces Where M = Cu, Ag, Au

The self-assembly behavior of a V-shaped bispyridine, 1,3-bi(4-pyridyl)benzene (BPyB), was studied by scanning tunneling microscopy on the (111) surfaces of Cu, Ag, and Au. BPyB molecules coordinately bonded with active Cu adatoms on Cu(111) in the form of complete polygonal rings at low coverages. On Ag(111), BPyB molecules aggregated into two-dimensional islands by relatively weak intermolecular hydrogen bonds. The coexistence of hydrogen bonds and coordination interaction was observed on the BPyB-covered Au(111) substrate. Density functional theory calculations of the metal-molecule binding energy and Monte Carlo simulations were performed to help understand the forming mechanism of molecular superstructures on the surfaces. In particular, the comprehensive orbital composition analysis interprets the observed metal-organic complexes and reveals the importance of relativistic effects for the extraordinary activity of gold adatoms. The relativistic effects cause the energy stability of the Au 6s atomic orbital and decrease the energy separation between the Au 6s and 5d orbitals. The enhanced sd hybridization strengthens the N-Au-N bond in BPyB-Au-BPyB complexes.

Dichotomous On-Surface Self-Assembly of Tripod Molecules with Anchor Like Interaction Pattern

Recent development of methods to fabricate low dimensional molecular structures has enabled tailoring their architecture using building blocks with suitably encoded structural and chemical properties. In this contribution we study structure formation in adsorbed assemblies comprising model tripod molecules equipped with terminal arm segments providing short-range directional interactions. The interaction directions were assigned in a specific anchor like pattern which enabled the creation of diverse intermolecular connections. To explore the on-surface self-assembly of these functional units the coarse grained lattice Monte Carlo simulation method was used in which the molecules were represented as collections of interconnected segments adsorbed on a triangular lattice. Our theoretical investigations focus on the effect of symmetry and size of molecular backbone on the outcome of the 2D self-assembly. The simulations revealed the formation of complex superstructures of two types including porous networks with diverse nanocavities and nanoribbons characterized by a constant width. Occurrence of these different assemblies was found to be strongly dependent on the molecular symmetry and aspect ratio, highlighting the decisive role of the arm length distribution in the tripod building block. The theoretical results of this study can be helpful in designing new low-dimensional superstructures which are stabilized be weak intermolecular interactions as well as by covalent bonds formed in on-surface reactions such as the Ullmann coupling.