Two-dimensional tessellation by molecular tiles constructed from halogen–halogen and halogen–metal networks

Abstract

Molecular tessellations are often discovered serendipitously, and the mechanisms by which specific molecules can be tiled seamlessly to form periodic tessellation remain unclear. Fabrication of molecular tessellation with higher symmetry compared with traditional Bravais lattices promises potential applications as photonic crystals. Here, we demonstrate that highly complex tessellation can be constructed on Au(111) from a single molecular building block, hexakis(4-iodophenyl)benzene (HPBI). HPBI gives rise to two self-assembly phases on Au(111) that possess the same geometric symmetry but different packing densities, on account of the presence of halogen-bonded and halogen–metal coordinated networks. Sub-domains of these phases with self-similarity serve as tiles in the periodic tessellations to express polygons consisting of parallelograms and two types of triangles. Our work highlights the important principle of constructing multiple phases with self-similarity from a single building block, which may constitute a new route to construct complex tessellations.

Complex k-uniform tilings by a simple bitopic precursor self-assembled on Ag(001) surface

“…Finally, we discuss the origin of these complex tilings. Previously, the Archimedean (1-uniform) tilings were realized from a single molecule featuring either two distinct functional centers that formed a single binding motif in complex tesselation 25 or by mixing two molecular phases that resulted in forming a new vertex type not present in the pure phases 26 .…”

“…The recent progress in the experimental realization of complex surface tessellations on an atomic and molecular level [7][8][9][10][11][12][13][14] is driven by the intriguing physical [15][16][17][18][19][20][21][22] and chemical 23 properties of these systems. In this respect, the supramolecular chemistry offers tools for engineering of distinct self-assembled surface geometries that present an expression of semiregular [24][25][26][27][28][29][30] , fractal [31][32][33][34][35] , quasicrystalline [36][37][38][39] , and random [3][4][5][6] tilings. Despite this effort, complex k-uniform tilings comprising a higher number of vertex types remain largely unexplored.…”

Design of Patchy Rhombi: From Close-Packed Tilings to Open Lattices

“…The formation of complex surface patterns at the molecular scale relies on the hierarchical assembly of organic functional molecules to self assembled monolayers on solid substrates, such as graphite or metallic surfaces [13,14]. Such assemblies of molecular species that lie flat on relatively inert substrates mostly result from reversible non-covalent interactions: self-similar, fractal aggregates, nonporous -ordered as well as disorderednetworks and even quasi-crystalline patterns emerge due to hydrogen [14][15][16][17][18] or halogen [19,20] bonding or van der Waals interactions [21,22]. Beyond the atomic details, a combination of simple factors fully describes the selfassembly of many different surface patterns: the geometric features of the building units, such as the aspect ratio or the rotational symmetry of the molecules, together with the placement of the bonding groups and possible * Electronic address: carina.karner@univie.ac.at † Electronic address: emanuela.bianchi@tuwien.ac.at energy differences between binding groups mostly determine the features of the assembled monolayers [23][24][25].…”

Snapshots of Dynamic Adaptation: Two‐Dimensional Molecular Architectonics with Linear Bis‐Hydroxamic Acid Modules

“…In particular, the modular assembly of intricate structures and the associated design principles are posing a current challenge in this area. Recent breakthroughs include the concept of self‐similarity expressed in intermolecular interactions, which lead to fractal structures and high‐order supramolecular networks . Additionally, the use of the extended coordination sphere of certain metal atoms, such as lanthanides, enabled the construction of Archimedean tessellations and 2D quasicrystals by the formation of well‐defined nodes…”