Evolution of Br⋯Br contacts in enantioselective molecular recognition during chiral 2D crystallization

Yi, Zhen-Yu; Yang, Xueqing; Duan, Jun-Jie; Zhou, Xiong; Chen, Ting; Wang, Dong; Li, Wan

doi:10.1038/s41467-022-33446-y

Cited by 15 publications

(15 citation statements)

References 50 publications

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“…In the following content, we discuss the chirality transfer and symmetry breaking occurring in three assembled structures. As previously reported, [ 51–53 ] both chiral and achiral molecules can be employed as building blocks for chiral assembly. Note, the building block of these assemblies is digly molecule, which is achiral but with asymmetric H‐bond configurations.…”

Section: Resultsmentioning

confidence: 83%

Kinetic Controlled Chirality Transfer and Induction in 2D Hydrogen‐Bonding Assemblies of Glycylglycine on Au(111)

Zhang

Ding

Shu

et al. 2023

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systems, such as the transfer and storage of genetic information in nucleic acids and the folding of proteins, while its origin remains as a major mystery. [1] For example, proteins are solely composed by l-amino acids, and nucleic acids (DNA and RNAs) are comprised of d-sugars. On the other hand, the chiral symmetry breaking process leads to many compelling observations in supramolecular chemistry, showing the spontaneous emerging of an enantiomeric entity by chiral self-assembly from an achiral molecule or the crystallization with a chiral space group. [2][3][4][5][6][7] More intriguingly, external physical stimulations, e.g. polarized light, [8][9][10] mechanical forces, [5,[11][12][13][14][15] could trigger a spontaneous symmetry breaking process towards a deterministic enantioselection, instead of adopting a stochastic process when no external force is applied. [3,7,16] Not only that, chiral self-assembly of biological substances has been also applied to fabricate various well-ordered nanostructures, such as helical nanotubes, [17][18][19][20] nanobelts, [21] and nanofibers, [22,23] based on noncovalent interactions. The chiral self-organization of small peptides, [24][25][26][27] especially the dipeptide-based nanotube, has been synthesized. [28] The dipeptides are excellent motifs in the fabrication of highly ordered biological structures owing to ease Chirality transfer is of vital importance that dominates the structure and functionality of biological systems and living matters. External physical stimulations, e.g. polarized light and mechanical forces, can trigger the chirality symmetry breaking, leading to the appearance of the enantiomeric entities created from a chiral self-assembly of achiral molecule. Here, several 2D assemblies with different chirality, synthesized on Au(111) surface by using achiral building blocks -glycylglycine (digly), the simplest polypeptide are reported. By delicately tuning the kinetic factors, i.e., one-step slow/rapid deposition, or stepwise slow deposition with mild annealing, achiral square hydrogen-bond organic frameworks (HOF), homochiral rhombic HOF and racemic rectangular assembly are achieved, respectively. Chirality induction and related symmetry broken in assemblies are introduced by the handedness (H-bond configurations in principle) of the assembled motifs and then amplified to the entire assemblies via the interaction between motifs. The results show that the chirality transfer and induction of biological assemblies can be tuned by altering the kinetic factors instead of applying external forces, which may offer an in-depth understanding and practical approach to peptide chiral assembly on the surfaces and can further facilitate the design of desired complex biomolecular superstructures.

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Section: Resultsmentioning

confidence: 83%

Kinetic Controlled Chirality Transfer and Induction in 2D Hydrogen‐Bonding Assemblies of Glycylglycine on Au(111)

Zhang

Ding

Shu

et al. 2023

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“…As listed in Figure S5c, the binding energy of structure I (−2.80 eV/molecule) is lower than that of structure II (−2.72 eV/molecule), indicating that structure I is more stable than structure II (the intermolecular binding energy is defined as E binding = ( E total – E mol – E base )/ n , where E total represents the total energy of the system, E molecular represents the energy of TBBI molecules, E base represents the energy of the Au-base, and n represents the number of molecules). According to previous studies, , it is not difficult to know that the assembly structure mainly depends on the competition between molecular flux onto the substrate and molecular diffusion on the substrate . When the coverage is 0.61 ± 0.02 ML, there is sufficient space for the precursors to relax and diffuse on the surface.…”

Section: Resultsmentioning

confidence: 99%

Coverage Modulated Transformation of the Supramolecular Assembly Structure of Brominated N-Heterocyclic Molecules on Au(111) Surfaces

Geng

Yang

et al. 2023

J. Phys. Chem. C

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Using brominated N-heterocyclic molecules with different lengths 4,4′,7,7′-tetrabromo-1H,1′H-2,2′-bibenzo[d]imidazole (TBBI) and 1,4-bis(4,7-dibromo-1H-benzo[d]imidazol-2-yl) benzene (DBBIB), we successfully constructed and characterized several large-area supramolecular assembly structures on Au(111) surfaces by molecular beam epitaxy and bond-resolved scanning tunneling microscopy. At low coverage (sub-monolayer), both molecules tend to form energetically favorable supramolecular assembly structures. At high coverage (full layer), TBBI can be assembled into grid-like structures with higher space utilization but less non-covalent interactions. However, the transition-like structure of DBBIB assembly with insufficient diffusion can also be kinetically captured at a high deposition rate. In addition, the hindrance between H atoms caused by the spatial configuration of different precursors also affects the self-assembly behavior of molecules. Density functional theory calculations suggest that the formation of various 2D supramolecular assembly structures is due to two types of halogen bonds (Br••• Br and Br•••N halogen bonds) and H•••Br/ H•••N hydrogen bonds. It is undeniable that this strategy can effectively provide a potential route for constructing more supramolecular nanostructures, which may influence the future design of molecular nanomaterials.

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“…In addition, they also do not belong to the solid solution [18] as they are periodic in one direction. Instead, they are a rare type of 1D disordered racemates [13a,14, 19] . This structure is characterized by having the chiral molecules arranged into 1D periodic homochiral stacks that are randomly mixed in the monolayer, thus making the overall structure aperiodic.…”

Section: From Dpp‐c12 Dimers To Tetramersmentioning

confidence: 99%

“…A 2D solid solution contains a random mixture of enantiomers that do not segregate into separate domains [12–13] . There exists a special and rarely reported structure known as a 1D disordered racemate based on the difference in the degree of order in molecular packing between racemates and random solid solutions [13a,14] . This structure is characterized by chiral molecules arranged periodically in one direction with a handedness, but without long‐range order in the arrangement of the two enantiomers along the perpendicular direction.…”

Section: Introductionmentioning

confidence: 99%

From One‐Dimensional Disordered Racemate to Ordered Racemic Conglomerates through Metal‐Coordination‐Driven Self‐Assembly at the Liquid‐Solid Interface

Hu,

Minoia,

Velpula

et al. 2023

Chemistry A European J

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In recent years, there has been significant focus on investigating and controlling chiral self‐assembly, specifically in the context of enantiomeric separation. This study explores the self‐assembly behavior of 4‐dodecyl‐3,6‐di(2‐pyridyl)pyridazine (DPP‐C12) at the interface between heptanoic acid (HA) and highly oriented pyrolytic graphite (HOPG) using a combination of scanning tunneling microscopy (STM) and multiscale molecular modeling. The self‐assembled monolayer structure formed by DPP‐C12 is periodic in one direction, but aperiodic in the direction orthogonal to it. These structures resemble 1D disordered racemic compounds. Upon introducing palladium [Pd(II)] ions, complexing with DPP‐C12, these 1D disordered racemic compounds spontaneously transform into 2D racemic conglomerates, which is rationalized with the assistance of force‐field simulations. Our findings provide insights into the regulation of two‐dimensional chirality.

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Evolution of Br⋯Br contacts in enantioselective molecular recognition during chiral 2D crystallization

Cited by 15 publications

References 50 publications

Kinetic Controlled Chirality Transfer and Induction in 2D Hydrogen‐Bonding Assemblies of Glycylglycine on Au(111)

Kinetic Controlled Chirality Transfer and Induction in 2D Hydrogen‐Bonding Assemblies of Glycylglycine on Au(111)

Coverage Modulated Transformation of the Supramolecular Assembly Structure of Brominated N-Heterocyclic Molecules on Au(111) Surfaces

From One‐Dimensional Disordered Racemate to Ordered Racemic Conglomerates through Metal‐Coordination‐Driven Self‐Assembly at the Liquid‐Solid Interface

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