Modeling of Close-Packed Patterns of Intact and Partially Deprotonated TPTC Molecules

Ibenskas, Andrius; Tornau, Evaldas E.

doi:10.1021/acs.jpcc.3c04593

Cited by 1 publication

(1 citation statement)

References 51 publications

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“…To facilitate the design of low-dimensional polymeric constructs formed on surfaces, computer-aided methods have recently been used. This refers especially to quantum chemical calculations focusing on bonding mechanisms and reaction paths of polymer formation [15,17] and to more self-assembly-oriented methods, such as the Monte Carlo [18][19][20][21][22] and molecular dynamics [23] simulations. While quantum methods (e.g., density functional theory, DFT) correspond to zero-Kelvin temperature and are usually limited to a few adsorbed molecules (interacting pairs or clusters), MC calculations allow for modeling of large molecular assemblies comprising thousands of units at finite temperatures.…”

Section: Introductionmentioning

confidence: 99%

Predicting Organometallic Intermediates in the Surface-Assisted Ullmann Coupling of Chrysene Isomers

Lisiecki,

Szabelski

2024

Molecules

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On-surface polymerization of functional organic molecules has been recently recognized as a promising route to persistent low-dimensional structures with tailorable properties. In this contribution, using the coarse-grained Monte Carlo simulation method, we study the initial stage of the Ullmann coupling of doubly halogenated chrysene isomers adsorbed on a catalytically active (111) crystalline surface. To that end, we focus on the formation of labile metal-organic precursor structures preceding the covalent bonding of chrysene monomers. Four monomeric chrysene units with differently distributed halogen substituents were probed in the simulations, and the resulting precursor structures were compared and quantified. Moreover, the effect of (pro)chirality of chrysene tectons on the structure formation was elucidated by running separate simulations in enantiopure and racemic systems. The calculations showed that suitable manipulation of the halogen substitution pattern allows for the creation of diverse precursor architectures, ranging from straight and winded chains to cyclic oligomers with enantiopure, racemic, and nonracemic composition. The obtained findings can be helpful in developing synthetic strategies for covalent polymers with predefined architecture and functionality.

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