Chirality variation from self-assembly on Ullmann coupling for the DBCh adsorbate on Au(111) and Ag(111)

Wang, Hongbing; Hu, Jielun; Liang, Zhaofeng; Zhang, Huan; Huang, Chaoqin; Xie, Lei; Jiang, Zheng; Huang, Han; Song, Fei

doi:10.1039/d2na00789d

Cited by 10 publications

(15 citation statements)

References 47 publications

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“…Note that because of the shorter fragment, which separates active centres in a molecule of c28 (two segments), and the presence of the protruding side segments, the resulting chains were less winded, as compared to the tetracene unit from Figure 1 . The structures shown in panel B of the figure were in full agreement with the experimental results obtained recently for the Ullmann coupling of 6,12-dibromochrysene on the Au(111) surface [ 48 ]. The average chain length calculated for rac - c28 was equal to 29.46 (see Figure S2 ).…”

Section: Resultssupporting

confidence: 89%

Structural Quantification of the Surface-Confined Metal-Organic Precursors Simulated with the Lattice Monte Carlo Method

Lisiecki

Szabelski

2023

Molecules

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The diversity of surface-confined metal-organic precursor structures, which recently have been observed experimentally, poses a question of how the individual properties of a molecular building block determine those of the resulting superstructure. To answer this question, we use the Monte Carlo simulation technique to model the self-assembly of metal-organic precursors that precede the covalent polymerization of halogenated PAH isomers. For this purpose, a few representative examples of low-dimensional constructs were studied, and their basic structural features were quantified using such descriptors as the orientational order parameter, radial distribution function, and one- and two-dimensional structure factors. The obtained results demonstrated that the morphology of the precursor (and thus the subsequent polymer) could be effectively tuned by a suitable choice of molecular parameters, including size, shape, and intramolecular distribution of halogen substituents. Moreover, our theoretical investigations showed the effect of the main structural features of the precursors on the related indirect characteristics of these constructs. The results reported herein can be helpful in the custom designing and characterization of low-dimensional polymers with adjustable properties.

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Section: Resultssupporting

confidence: 89%

Structural Quantification of the Surface-Confined Metal-Organic Precursors Simulated with the Lattice Monte Carlo Method

Lisiecki

Szabelski

2023

Molecules

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“…In other words, these interactions, which can be weak or strong, were viewed as not affecting the directionality of the intermolecular connections stabilizing the triangular aggregates. However, the above assumption, even though it may seem too far, was proved to be correct for numerous self-assembling systems of surfaces. ,− For those real systems adsorbed on such substrates, Au(111), Ag(111), and Cu(111), it was observed that the emerging structures were topologically identical to their theoretical counterparts. The only difference was the relative in-plane rotation/shift of the aggregates with respect to the main lattice directions induced by the mismatch of the overlayer and the substrate.…”

Section: Discussionmentioning

confidence: 99%

Toward Molecular Fractals on Surfaces: Designing Covalent Structures with the Monte Carlo Simulation Method

Szabelski,

Lisiecki

2023

J. Phys. Chem. C

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Deterministic fractals have long been considered abstract objects with unique structural properties, and their experimental realization by systematic molecular design has been achieved only recently. In this contribution, we demonstrate how the coarse-grained Monte Carlo modeling can be used to predict and optimize the formation of the fractal Sierpinśki-type triangular metal−organic precursors on solid substrates. To that end, a mixture of suitably functionalized polyaromatics differing in size/ shape and bivalent metal atoms adsorbed on a (111) crystalline surface was modeled. These theoretical investigations focused on the surface-assisted self-assembly of labile precursor architectures preceding the covalent linkage of halogenated aryl monomers in Ullmann-type coupling reactions. Our calculations aimed at the identification of all of the isomers from a large group of candidate units capable of forming fractal triangles and classification of these superstructures. With the collected data, it was possible to extract common molecular features, which made the diverse building blocks able to create topologically identical self-assembled constructs. As a result, we formulated a set of elementary prerequirements that have to be met by an arbitrary functional unit to create the Sierpinśki triangles sustained by 2-fold metal−organic nodes (and subsequent covalent bonds). Our findings are quite general and can be applied to various molecular tectons equipped with active groups providing directional interactions of other types (e.g., hydrogen bonding). This information can be helpful in the design and fabrication of new persistent fractal macromolecules with yet unexplored physicochemical properties.

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“…A great number of chiral assemblies have been studied on metal surfaces, including 0D chiral clusters, [24][25][26][27] 1D chiral chains, stripes or lines, filaments, wires [28][29][30][31][32][33][34] and 2D chiral islands, lamellas structures and honeycomb or more complex nontrivial architectures (chiral Kagome networks, quasicrystals, Sierpiński triangle fractals and semi-regular Archimedean tilings) that may possess intriguing physical and chemical properties. Most of these chiral nanostructures are achieved through shortrange chiral recognition induced by non-covalent intermolecular interactions, such as hydrogen bonding, [24,28,30,31,[34][35][36][37][38][39][40][41][42] halogen bonding, [33,[43][44][45][46] van der Waals (vdW) forces, [47] dipoledipole interactions, [48] metal-organic coordination [33,[49][50][51] or cooperative interactions of two or more sorts of intermolecular forces. [27,29,34,40,[52][53][54][55] In addition, the competition between molecule-molecule an...…”

Section: Chiral Assemblies Induced By Short-range Chiral Recognitionmentioning

confidence: 99%

From Short‐ to Long‐Range Chiral Recognition on Surfaces: Chiral Assembly and Synthesis

Peng,

Zhang,

Liu

et al. 2023

Small

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Research on chiral behaviors of small organic molecules at solid surfaces, including chiral assembly and synthesis, can not only help unravel the origin of the chiral phenomenon in biological/chemical systems but also provide promising strategies to build up unprecedented chiral surfaces or nanoarchitectures with advanced applications in novel nanomaterials/nanodevices. Understanding how molecular chirality is recognized is considered to be a mandatory basis for such studies. In this review, a series of recent studies in chiral assembly and synthesis at well‐defined metal surfaces under ultra‐high vacuum conditions are outlined. More importantly, the intrinsic mechanisms of chiral recognition are highlighted, including short/long‐range chiral recognition in chiral assembly and two main strategies to steer the reaction pathways and modulate selective synthesis of specific chiral products on surfaces.

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Chirality variation from self-assembly on Ullmann coupling for the DBCh adsorbate on Au(111) and Ag(111)

Abstract: On-surface Ullmann coupling has been witnessed as an appealing approach for the precise fabrication of carbon-based covalent nanostructures under the solution-free condition. However, chirality has been seldom discussed in Ullmann...

Cited by 10 publications

References 47 publications

Structural Quantification of the Surface-Confined Metal-Organic Precursors Simulated with the Lattice Monte Carlo Method

Structural Quantification of the Surface-Confined Metal-Organic Precursors Simulated with the Lattice Monte Carlo Method

Toward Molecular Fractals on Surfaces: Designing Covalent Structures with the Monte Carlo Simulation Method

From Short‐ to Long‐Range Chiral Recognition on Surfaces: Chiral Assembly and Synthesis

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