Surface‐Confined Self‐Assembly of Asymmetric Tetratopic Molecular Building Blocks

Abstract

Surface‐confined self‐assembly of functional molecular building blocks has recently been widely used to create low‐dimensional, also covalent, superstructures with tailorable geometry and physicochemical properties. In this contribution, using the lattice Monte Carlo simulation method, we demonstrate how the structure‐property relation can be established for the 2D self‐assembly of a model tetrapod molecule with reduced symmetry. To that end, a rigid functional unit comprising a few interconnected segments arranged in different tetrapod shapes was used and its self‐assembly on a triangular lattice representing a (111) crystal surface was simulated. The results of our calculations show strong dependence of the structure formation on the molecular symmetry, in particular on the (pro)chiral nature of the building block. The simulations predicted the formation of unusual ordered racemic networks with unique aperiodic spatial distribution of the surface enantiomers. Molecular symmetry was also found to have significant influence on the enantiopure self‐assembly which resulted in the Kagome and brickwall networks and other less ordered extended superstructures with parallelogram pores. The theoretical findings of this contribution can be relevant to designing and on‐surface synthesis of molecular superstructures with predefined geometries and functions. In particular, the predicted molecular architectures can stimulate experimental efforts to fabricate and explore new nanostructures, for example graphitic, having the composition and geometry proposed in our study.

Simple lattice model of surface-confined metal–organic networks consisting of linear nitrogen-bearing molecules and transition metals

“…This approach has shown to be applicable to the study of the phase behavior of both generalized SMON models and models specified for particular metal-organic layers. 4,[16][17][18][19][20][21][22][37][38][39][40][41] Generalized lattice models of SMONs make it possible to carry out a computational experiment for various SMONs under the same conditions, to compare the results, to reveal general patterns in their phase behavior and to extend them to a whole class of metal-organic layers. For instance, Gdula and Nieckarz 38 have established a set of phases formed by starshaped molecules and low-coordinating metal centers.…”

Self-assembly of s-indacene-tetrone on Cu(111): molecular trapping and patterning of Cu adatoms

“…Recently, a series of coarse-grained Monte Carlo simulations have been developed to interpret various two-dimensional molecular patterns, 42,43 especially for tetratomic molecules. [44][45][46] Here, numerical calculations based on the density functional theory (DFT) were performed to evidence the stability of the various coordination structures.…”

A Bidimensional Gay-Berne Calamitic Fluid: Structure and Phase Behavior in Bulk and Strongly Confined Systems

“…Production is scaled by merely increasing the amounts of reactants and relying on system kinetics for product formation. Packing specificity can be modulated by carrying out the assembly under spatial confinement [9][10][11][12][13][14][15]. Many fabrication protocols have been optimized by mimicking the strategies latent in biomolecular systems [4,16,17].…”