Monte Carlo Simulations of the Metal-Directed Self-Assembly of Y-Shaped Positional Isomers

Abstract

The rational fabrication of low-dimensional materials with a well-defined topology and functions is an incredibly important aspect of nanotechnology. In particular, the on-surface synthesis (OSS) methods based on the bottom-up approach enable a facile construction of sophisticated molecular architectures unattainable by traditional methods of wet chemistry. Among such supramolecular constructs, especially interesting are the surface-supported metal–organic networks (SMONs), composed of low-coordinated metal atoms and π-aromatic bridging linkers. In this work, the lattice Monte Carlo (MC) simulation technique was used to extract the chemical information encoded in a family of Y-shaped positional isomers co-adsorbed with trivalent metal atoms on a flat metallic surface with (111) geometry. Depending on the intramolecular distribution of active centers (within the simulated molecular bricks, we observed a metal-directed self-assembly of two-dimensional (2D) openwork patterns, aperiodic mosaics, and metal–organic ladders. The obtained theoretical findings could be especially relevant for the scanning tunneling microscopy (STM) experimentalists interested in a surface-assisted construction of complex nanomaterials stabilized by directional coordination bonds.

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

“…How is the phase behavior of the SMONs affected by the chemical structure of functional groups? This question has been answered in terms of the ability to form the coordination bond at different angles relative to the axis of the molecule in recent studies by D. Nieckarz et al 19–22…”

Ordering of monomers, dimers and polymers of deposited Br2I2Py molecules: a modeling study

“…MC calculations can be performed very efficiently using purposely built interaction models which recently proved their successful ability to study the assembly behavior of various small organic molecules with hydrogen and halogen bonds. 21–25…”

“…MC calculations can be performed very efficiently using purposely built interaction models which recently proved their successful ability to study the assembly behavior of various small organic molecules with hydrogen and halogen bonds. [21][22][23][24][25] In this work, we present the model for ordering of Br 2 I 2 Py molecules in two-dimensional, dimeric and polymeric structures. Using DFT calculations, we estimate two pair interaction energies responsible for two-dimensional ordering of intact molecules.…”

On-surface Ullmann coupling of halo-derivatives of arenes: Monte Carlo simulations for tetracene

“…This refers especially to the number and intramolecular distribution of halogen substituents in PAHs monomers, aiming at the synthesis of the polymer with predefined architecture. To facilitate the optimization of the monomeric units, computer-aided methods like quantum mechanical (QM) modelling, molecular dynamics (MD), and Monte Carlo (MC) simulations have often been applied [35][36][37][38][39][40][41][42][43][44][45]. While QM calculations have been used mainly to determine energetics and mechanisms of intermolecular bonding [35][36][37][38], the other methods have been much less widespread, and they have drawn considerable attention quite recently, in spite of better scaling properties and being relatively less complicated [39][40][41][42][43][44][45][46].…”

“…To facilitate the optimization of the monomeric units, computer-aided methods like quantum mechanical (QM) modelling, molecular dynamics (MD), and Monte Carlo (MC) simulations have often been applied [35][36][37][38][39][40][41][42][43][44][45]. While QM calculations have been used mainly to determine energetics and mechanisms of intermolecular bonding [35][36][37][38], the other methods have been much less widespread, and they have drawn considerable attention quite recently, in spite of better scaling properties and being relatively less complicated [39][40][41][42][43][44][45][46]. Among diverse computational chemistry tools, the coarse-grained MC simulations turned out to be an effective way of predicting the architecture of metal-organic intermediates, as confirmed by the corresponding experimental data -obtained, for example, with STM imaging of adsorbed overlayers [11][12][13][14].…”