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

Abstract

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.

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

“…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...…”

Two-dimensional self-assembly and co-assembly of two tetracarboxylic acid derivatives investigated by STM

“…are modied in the molecular structure to provide hydrogen bonding sites for intermolecular recognition. [12][13][14][15][16][17] Among them, the modication of carboxyl groups at the ends of benzene rings is a commonly used method for constructing hydrogen-bonded supramolecular assembly systems. [18][19][20] Molecular interaction sites are closely related to the number and substitution position of carboxyl groups, which inuences the molecular symmetry and the intermolecular interaction mode and further the nal self-assembly nanostructure.…”

Orientational Growth of Flexible van der Waals Supramolecular Networks

“…[ 19 ] The phase transition is explained by the competition between molecule–molecule and molecule surface interactions. [ 18 ] These nonhost–guest bicomponent networks on surfaces are widely studied in ultrahigh vacuum (UHV) [ 20 ] and under ambient conditions; [ 21 ] they can be categorized according to dominant intermolecular interactions in the stabilization of self‐assembly on surfaces, such as hydrogen bonding, [ 22 ] halogen bonding, [ 23 ] or metal–ligand coordination. [ 24 ] C 60 does not have functional groups; hence, its interaction with other molecules relies on cooperative interactions where the stability of 2D assemblies depends on the simultaneous interaction among many molecules instead of that of the nearest neighbor molecules.…”