Dichotomous Array of Chiral Quantum Corrals by a Self-Assembled Nanoporous Kagomé Network

Klappenberger, Florian; Kühne, Dirk; Krenner, Wolfgang; Silanes, Iñaki; Arnau, A.; Abajo, F. Javier García de; Klyatskaya, Svetlana; Rüben, Mario; Barth, Johannes V.

doi:10.1021/nl901700b

Cited by 81 publications

(120 citation statements)

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“…A potential pathway that could mediate a correlated dynamics is given by the indirect electronic interactions due to surface state scattering on the network and confined objects, which has been exploited to steer the alignment of adatoms in supramolecular gratings on the same substrate in the past (34,35). However, with these systems, there was similarly no evidence for a correlated translational motion or lateral organization in adjacent 1D furrows (34,35), presumably because there is little crosstalk between areas separated by molecular rims (34)(35)(36).…”

Section: Resultsmentioning

confidence: 99%

Rotational and constitutional dynamics of caged supramolecules

Kühne

Klappenberger²,

Krenner³

et al. 2010

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

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The confinement of molecular species in nanoscale environments leads to intriguing dynamic phenomena. Notably, the organization and rotational motions of individual molecules were controlled by carefully designed, fully supramolecular host architectures. Here we use an open 2D coordination network on a smooth metal surface to steer the self-assembly of discrete trimeric guest units, identified as noncovalently bound dynamers. Each caged chiral supramolecule performs concerted, chirality-preserving rotary motions within the template honeycomb pore, which are visualized and quantitatively analyzed using temperature-controlled scanning tunneling microscopy. Furthermore, with higher thermal energies, a constitutional system dynamics appears, which is revealed by monitoring repetitive switching events of the confined supramolecules' chirality signature, reflecting decay and reassembly of the caged units. supramolecular dynamics | nanochemistry | surface architecture T he dynamics of molecular species can be controlled by carefully designed, fully supramolecular host architectures, provided either as discrete capsules or extended nanoporous networks. It was recognized in particular that unique rotary motion phenomena of single molecular species can be encoded by such conditions (1-5). Moreover, with the restriction to surfaceconfined systems it became possible to investigate molecular rotation and noncovalent assembly processes of individual molecules adsorbed at surfaces by atomic-scale scanning tunneling microscopy (STM) (6-12). However, the direct observation of dynamic supramolecular entities in controlled environments remained elusive although this objective represents a key issue of supramolecular science and constitutional dynamic chemistry (13-16). Herein we report dynamic phenomena at the supramolecular level, resulting from the nanoscale confinement of a multicomponent aggregate in an open 2D coordination network on a smooth metal surface. The presented nanopores steer the assembly and cage the realized discrete 2D-chiral trimeric dynamers, whose behavior is directly monitored by temperaturecontrolled STM. We visualized and analyzed quantitatively their rotary motions, whereby the collective nature of the system dynamics is demonstrated by following chirality-preserving individual reorientation events. The findings reveal opportunities for the field of surface-mounted rotors, limited to single molecular units so far (17)(18)(19). Furthermore, we infer constitutional dynamics from the switching of the chirality signature for increased thermal energies, reflecting the repetitive decay and reassembly of the caged supramolecules. With our observations, a demonstrator for the intricate collective dynamics of caged supramolecular dynamers is provided.

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Section: Resultsmentioning

confidence: 99%

Rotational and constitutional dynamics of caged supramolecules

Kühne

Klappenberger²,

Krenner³

et al. 2010

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

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“…57 Chiral structure can also be achieved using achiral molecules. 1,54,55,58,59 In that case, the chirality results from the specific arrangement of the molecules. In the case of very small molecules made of few benzene rings, without alkyl chain and any specific substituant to drive intermolecular self-assembly, van der Waals interactions are expected to drive the formation of close-packed organic structures and the chirality of the resulting arrangements can hardly be predicted.…”

Section: ■ Introductionmentioning

confidence: 99%

Coexisting Chiral Two-Dimensional Self-Assembled Structures of 1,2,3,4-Tetrahydronaphthalene Molecules: Porous Pinwheel Nanoarchitecture and Close-Packed Herringbone Arrangement

2017

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International audienceThe self-assembly of 1,2,3,4-tetrahydronaph-thalene molecules is investigated using scanning tunneling microscopy (STM) at the solid/liquid interface. STM reveals that the molecule self-assembles into a chiral close-packed herringbone structure and a chiral porous pinwheel nano-architecture at room temperature on graphite. The two networks are equally distributed on the surface, and the two enantiomeric molecular arrangements of the two structures are observed. Variation of the molecule−surface epitaxial relationship suggests that the pinwheel arrangement favors molecule− surface interactions, whereas the herringbone arrangement favors intermolecular interactions

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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.…”

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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.

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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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Dichotomous Array of Chiral Quantum Corrals by a Self-Assembled Nanoporous Kagomé Network

Cited by 81 publications

References 28 publications

Rotational and constitutional dynamics of caged supramolecules

Rotational and constitutional dynamics of caged supramolecules

Coexisting Chiral Two-Dimensional Self-Assembled Structures of 1,2,3,4-Tetrahydronaphthalene Molecules: Porous Pinwheel Nanoarchitecture and Close-Packed Herringbone Arrangement

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

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