Tailoring long-range superlattice chirality in molecular self-assemblies <i>via</i> weak fluorine-mediated interactions

Telychko, Mykola; Wang, Lulu; Hsu, Chia-Hsiu; Li, Guangwu; Peng, Xinnan; Song, Shaotang; Su, Jie; Chuang, Feng‐Chuan; Wu, Jishan; Wong, Ming Wah; Lu, Jiong

doi:10.1039/d1cp02996g

Cited by 3 publications

(4 citation statements)

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“…From the distorted appearance, we have identified the L and R chiralities as shown in Figure a,b, respectively. Similar chiral identification has been also reported for HPB derivatives. − On the Au(111) surface, it should be noted again that the molecular chirality of the self-assembled Br 2 -HPB can be resolved only at 1.0 V < | V s | < 1.5 V. Figure c shows the chirality-resolved STM image of the self-assembled Br 2 -HPB layer, in which the dashed lines indicate the direction of the unit cell vector a ⃗ (along the bromophenyl-linked network). In this STM image, the L and R chiralities coexist as indicated by yellow and red round arrows, respectively, resulting in the formation of a two-dimensional racemic mixture.…”

Section: Resultssupporting

confidence: 75%

“…In addition, the molecular axis is misoriented by 16.5 ± 2.7° from a ⃗. Figure f shows the space-filling model of the unit cell, in which the Br 2 -HPB molecules are mutually interlocked, similar to propeller-shaped HPB molecules and its derivatives. ,− In the model, it should be noted that the molecular axis of Br 2 -HPB is well aligned as mentioned above, leading to the formation of the bromophenyl-linked one-dimensional network of Br 2 -HPB along the a ⃗ direction. Thus, this structure should be stabilized by the bromophenyl–bromophenyl interactions, as well as the mutual interlocking of the phenyl rings of neighboring molecules.…”

Section: Resultsmentioning

confidence: 89%

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Two-Step On-Surface Synthesis of One-Dimensional Nanographene Chains

2023

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Controllable fabrication of low-dimensional graphene structures is a matter of scientific and technological interest. To date, significant efforts have been devoted to the fabrication of nanographene chains as well as nanographenes and graphene nanoribbons. Here, we present the on-surface synthesis of one-dimensional (1D) nanographene chains composed of hexa-peri-hexabenzocoronene (HBC) which is a common type of nanographene. Using dibromo-substituted hexaphenylbenzene (Br2-HPB) as a precursor, the 1D HBC nanographene chains are achieved through two reaction steps, namely polymerization and cyclodehydrogenation, on a Au(111) surface, which have been investigated by low-temperature scanning tunneling microscopy. The Br2-HPB molecules deposited on Au(111) are formed into a chiral selective self-assembled layer, and the following thermal annealing at 200–300 °C induces debromination and sequential polymerization of Br2-HPB, leading to the formation of long 1D HPB chains. In particular, we find that the same length 1D HPB chains are selectively ordered in a side-by-side arrangement. Finally, by annealing at 400 °C, HBC planar nanographenes are achieved through the cyclodehydrogenation process of HPB within the long 1D chains. The maximum length of the obtained 1D HBC nanographene chains reached is about 30 nm.

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Section: Resultssupporting

confidence: 75%

Section: Resultsmentioning

confidence: 89%

Two-Step On-Surface Synthesis of One-Dimensional Nanographene Chains

2023

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“…The halobenzene is the simplest halogenated aromatic molecule, while 1,3,5-trihalobenzene, with three extension directions, is the simplest halogenated aromatic molecule to form the 2D monolayers. The halogen species studied are Cl, Br, and I, while F is excluded as its σ hole is very weak or nonexisting, and the F···F interaction is mostly repulsive. , The Cu(111) surface was investigated as it is the most compact and lowest-energy surface of copper.…”

Section: Introductionmentioning

confidence: 99%

Dispersion-Corrected DFT-D4 Study of the Adsorption of Halobenzenes and 1,3,5-Trihalobenzenes on the Cu(111) Surface─Effect of Sigma Hole Properties

et al. 2023

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Halogen bonds, characterized by directionality, tunability, hydrophobicity, and variable sizes, are ideal noncovalent interactions to design and control the formation of self-assembled nanostructures. The specific self-assembly cases formed by the halogen-bonding interaction have been well studied by scanning tunneling microscopy (STM) experiments and density functional theory (DFT) calculations. However, there is a lack of systematic theoretical adsorption studies on halogenated molecules. In this work, the adsorption of halobenzenes and 1,3,5-trihalobenzenes on the Cu(111) surface was examined by dispersion-corrected DFT methods. The adsorption geometries, noncovalent molecule–surface interactions, electronic densities, and electrostatic potential maps were examined for their most stable adsorption sites using the DFT-D4 method. Our calculations revealed that the iodo compounds favor a different adsorption geometry from aryl chlorides and bromides. Down the halogen group (Cl to I), the adsorption energy increases and the distance between the halogen atom and Cu surface decreases, which indicates stronger molecule–surface interactions. This is supported by the changes in the density of states upon adsorption. Noncovalent interaction analysis was also employed to further understand the nature and relative strength of the molecule–surface interactions. Electrostatic potential maps revealed that the positive character of the halogen sigma hole becomes stronger upon adsorption. Thus, surface adsorption of the halogenated molecule will enhance the formation of intermolecular halogen bonds. The present theoretical findings are expected to contribute toward a more comprehensive understanding of halogen bonding on the Cu(111) surface.

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“…Chirality, a fundamental phenomenon in the nature intricately connected to the origins of life, has gained extensive interests within the scientific community. − The investigation of the chirality of organic molecules on solid surfaces constitutes a crucial area encompassing enantioselective catalysis, chiral separation, and advancements in sensor technologies. − When chiral molecules are adsorbed onto solid surfaces, they exhibit diverse configurations, forming conglomerates, racemates, or enantiomeric solutions . The formation of chiral nanostructures is a complex process modulated by the interplay between intermolecular interactions and molecule–substrate interactions. − In general, the interaction between molecules and the presence of the steric hindrance effect leads to a preference for specific energetically favorable configurations. , However, a thorough understanding of how these interactions influence the molecular chiral arrangement still remains elusive …”

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confidence: 99%

Selective Formation of Homochiral Dimers by Intermolecular Charge Transfer on a hBN Nanomesh

Hao,

Zhang,

Niu

et al. 2024

ACS Nano

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In this study, a comprehensive characterization was conducted on a chiral starburst molecule (C 57 H 48 N 4 , SBM) using scanning tunneling microscopy. When adsorbed onto the hBN/Rh(111) nanomesh, these molecules demonstrate homochiral recognition, leading to a selective formation of homochiral dimers. Further tip manipulation experiments reveal that the chiral dimers are stable and primarily controlled by strong intermolecular interactions. Density functional theory (DFT) calculations supported that the chiral recognition of SBM molecules is governed by the intermolecular charge transfer mechanism, different from the common steric hindrance effect. This study emphasizes the importance of intermolecular charge transfer interactions, offering valuable insights into the chiral recognition of a simple bimolecular system. These findings hold significance for the future advancement in chirality-based electronic sensors and pharmaceuticals, where the chirality of molecules can impact their properties.

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Tailoring long-range superlattice chirality in molecular self-assemblies via weak fluorine-mediated interactions

Abstract: Controllable fabrication of the enantiospecific molecular superlattices is a matter of imminent scientific and technological interest. Herein, we demonstrate that long-range superlattice chirality in molecular self-assemblies can be tailored by...

Cited by 3 publications

References 60 publications

Two-Step On-Surface Synthesis of One-Dimensional Nanographene Chains

Two-Step On-Surface Synthesis of One-Dimensional Nanographene Chains

Dispersion-Corrected DFT-D4 Study of the Adsorption of Halobenzenes and 1,3,5-Trihalobenzenes on the Cu(111) Surface─Effect of Sigma Hole Properties

Selective Formation of Homochiral Dimers by Intermolecular Charge Transfer on a hBN Nanomesh

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