Chiral Kagomé Lattice from Simple Ditopic Molecular Bricks

Schlickum, Uta; Decker, Régis; Klappenberger, Florian; Zoppellaro, Giorgio; Klyatskaya, Svetlana; Auwärter, Willi; Neppl, Stefan; Kern, Klaus; Brune, Harald; Rüben, Mario; Barth, Johannes V.

doi:10.1021/ja8028119

Cited by 194 publications

(233 citation statements)

References 54 publications

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“…A prominent example is dicyanoquinquiphenyl on Ag(111), which forms a chiral Kagomé mesh because of a combination of hydrogen bonding and antiparallel dipole alignment of the nitrile groups (Fig. 14d) [88]. Mirror-symmetry breaking was also observed in metalorganic networks of iron terephthalate on Cu(110).…”

Section: Perturbation Of Parity Eigenstates In 1927mentioning

confidence: 98%

Molecular chirality at surfaces

Ernst

2012

Physica Status Solidi (b)

219

261

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With the adsorption of larger molecules being increasingly tackled by surface scientists, the aspect of chirality often plays a role. This paper gives a topical review of molecular chirality at surfaces and gives a phenomenological overview of different aspects of adsorption and self‐assembly of chiral and prochiral molecules and the principles of mirror‐symmetry breaking at a surface. After a brief introduction into the history of molecular chirality and the important role it played for understanding the spatial structure of molecules, definitions of chirality are presented. Topics treated here are principle ways to create single chiral adsorbates, chiral ensembles, and monolayers by achiral molecules, adsorption of intrinsically chiral molecules at achiral and chiral surfaces, long‐range symmetry breaking in two‐dimensional (2D) crystals due to additional chiral bias, chiral restructuring of solid surfaces under the influence of chiral molecules, switching the handedness of adsorbates, and chirality at the liquid/air interface. An outlook onto further potential research directions and recommendations for further reading, including nonsurface‐related sources of chiral topics completes this paper.

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Section: Perturbation Of Parity Eigenstates In 1927mentioning

confidence: 98%

Molecular chirality at surfaces

Ernst

2012

Physica Status Solidi (b)

219

261

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“…A conformational adaptation similar to the one found here also played an important role herein during the assembly of linear molecules into a chiral KagomØ lattice. [18] A qualitative change of the bonding type resulting in unconventional motifs was equally encountered in metal-directed assembly at surfaces. [35] …”

Section: Conformational Adaptationmentioning

confidence: 99%

“…[3,8,10,[13][14][15] The restriction to a substrate not only modifies existing chiral properties, but novel and interesting chiral effects that are not possible for bulk materials also arise. [7,14,[16][17][18] Moreover, the interaction with the metal substrate can dictate a new conformation that differs remarkably from the geometry exhibited in the crystal phase and changes the functionality, as often experienced for porphyrins [19] and adaptive peptide or amino acid species. [7,20,21] Herein we report a multi-technique study of an oxalic amide derivative featuring the functional amide group that potentially forms hydrogen-bond motifs pivotal for the tertiary structures of a large number of biomolecules, in particular peptides.…”

Section: Introductionmentioning

confidence: 99%

Does the Surface Matter? Hydrogen‐Bonded Chain Formation of an Oxalic Amide Derivative in a Two‐ and Three‐Dimensional Environment

et al. 2008

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We report on a multi‐technique investigation of the supramolecular organisation of N,N‐diphenyl oxalic amide under differently dimensioned environments, namely three‐dimensional (3D) in the bulk crystal, and in two dimensions on the Ag(111) surface as well as on the reconstructed Au(111) surface. With the help of X‐ray structure analysis and scanning tunneling microscopy (STM) we find that the molecules organize in hydrogen‐bonded chains with the bonding motif qualitatively changed by the surface confinement. In two dimensions, the chains exhibit enantiomorphic order even though they consist of a racemic mixture of chiral entities. By a combination of the STM data with near‐edge X‐ray absorption fine‐structure spectroscopy, we show that the conformation of the molecule adapts such that the local registry of the functional group with the substrate is optimized while avoiding steric hindrance of the phenyl groups. In the low coverage case, the length of the chains is limited by the Au(111) reconstruction lines restricting the molecules into fcc stacked areas. A kinetic Monte Carlo simulated annealing is used to explain the selective assembly in the fcc stacked regions.

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“…They may represent geometrically frustrated magnets (7) or provide novel routes for constructing photonic crystals (8). However, with the exception of the frequently realized trihexagonal tiling (also known as the Kagomé lattice) (9)(10)(11)(12)(13)(14)(15), the other semiregular Archimedean tiling patterns remain largely unexplored.…”

mentioning

confidence: 99%

“…Self-assembly protocols have been developed to achieve regular surface tessellations, including the semiregular Kagomé lattice (11)(12)(13), and even more complex tiling patterns or surface decorations (25)(26)(27)(28)(29)(30). Despite the striking advances, five-vertex structures remain a challenging issue, reflecting the lack of adequate complementary polygonal molecular modules and planar fivefold coordination nodes, respectively.…”

mentioning

confidence: 99%

Five-vertex Archimedean surface tessellation by lanthanide-directed molecular self-assembly

Écija

Urgel

Papageorgiou

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

127

109

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The tessellation of the Euclidean plane by regular polygons has been contemplated since ancient times and presents intriguing aspects embracing mathematics, art, and crystallography. Significant efforts were devoted to engineer specific 2D interfacial tessellations at the molecular level, but periodic patterns with distinct five-vertex motifs remained elusive. Here, we report a direct scanning tunneling microscopy investigation on the ceriumdirected assembly of linear polyphenyl molecular linkers with terminal carbonitrile groups on a smooth Ag(111) noble-metal surface. We demonstrate the spontaneous formation of fivefold Celigand coordination motifs, which are planar and flexible, such that vertices connecting simultaneously trigonal and square polygons can be expressed. By tuning the concentration and the stoichiometric ratio of rare-earth metal centers to ligands, a hierarchic assembly with dodecameric units and a surface-confined metalorganic coordination network yielding the semiregular Archimedean snub square tiling could be fabricated.T he tiling of surfaces is relevant for pure art (1), mathematics (2, 3), material physics (4), and molecular science (5). Johannes Kepler's pertaining, rigorous analysis revealed four centuries ago that in the Euclidean plane 11 tessellations based on symmetric polygonal units exist (6): three consist of a specific polygon (so-called regular tilings with squares, triangles, or hexagons, respectively), whereas eight require the combination of two or more different polygons (named semiregular or Archimedean tilings from triangles, squares, hexagons, octagons, and dodecagons).Manifestations of regular tessellations at the atomic and molecular level are ubiquitous, including crystalline planes and surfaces of elemental or molecular crystals, and honeycomb structures encountered, e.g., for graphene sheets, strain relief and supramolecular lattices. In addition, the family of semiregular Archimedean tilings features intriguing characteristics. They may represent geometrically frustrated magnets (7) or provide novel routes for constructing photonic crystals (8). However, with the exception of the frequently realized trihexagonal tiling (also known as the Kagomé lattice) (9-15), the other semiregular Archimedean tiling patterns remain largely unexplored.Three of the semiregular Archimedean tilings correspond to five-vertex configurations (Fig. 1 A-C): the snub hexagonal tiling (four triangles and one hexagon at each vertex, labeled 3.3.3.3.6), the elongated triangular tiling (three triangles and two squares join at each vertex in a 3.3.3.4.4 sequence), and the snub square tiling (three triangles and two squares at each vertex; labeled 3.3.4.3.4). They have been identified in bulk materials, such as layered crystalline structures of complex metallic alloys (4, 16-18), supramolecular dendritic liquids (19), liquid crystals (20), special star-branched polymers (21, 22), and binary nanoparticle superlattices (23). Moreover, recent experiments with colloids at a quasicrystalline substra...

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Chiral Kagomé Lattice from Simple Ditopic Molecular Bricks

Cited by 194 publications

References 54 publications

Molecular chirality at surfaces

Molecular chirality at surfaces

Does the Surface Matter? Hydrogen‐Bonded Chain Formation of an Oxalic Amide Derivative in a Two‐ and Three‐Dimensional Environment

Five-vertex Archimedean surface tessellation by lanthanide-directed molecular self-assembly

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